Benzocycle-substituted triazine and pyrimidine ultraviolet light absorbers

ABSTRACT

This invention relates generally to benzocycle-substituted pyrimidines and triazines and the use thereof to protect against degradation by environmental forces, inclusive of ultraviolet light, actinic radiation, oxidation, moisture, atmospheric pollutants and combinations thereof. The new class of benzocycle-substituted pyrimidines and triazines comprises a benzocycle attached to the triazine or pyrimidine ring, and preferably an additional aryl ring containing a hydroxyl group, either free or blocked to form a latent stabilizer, ortho- to the point of attachment to the triazine or pyrimidine ring. These materials may, under the appropriate circumstances, be bonded to formulations comprising coatings, polymers, resins, organic compounds and the like via reaction of the bondable functionality with the materials of the formulation. A method for stabilizing a material by incorporating such benzocycle-substituted pyrimidines and triazines is also disclosed.

This application claims the benefit of U.S. Provisional application No.60/090,260 filed on Jun. 22, 1998 and U.S. Provisional application No.60/108,895 filed on Apr. 17, 1998.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates generally to novel benzocycle-substitutedpyrimidines and triazines and their use as protectants againstdegradation by environmental forces, including ultraviolet light,actinic radiation, oxygen, moisture, atmospheric pollutants andcombinations thereof.

2. Description of Related Art

Exposure to sunlight and other sources of ultraviolet radiation is knownto cause degradation of a variety of materials, especially polymericmaterials. For example, polymeric materials such as plastics oftendiscolor and may become brittle as a result of exposure to ultravioletlight. Accordingly, a large body of art has been developed directedtowards materials such as ultraviolet light absorbers and stabilizerswhich are capable of inhibiting such degradation.

A class of materials known to be ultraviolet light absorbers areo-hydroxyphenyltriazines, in which at least one substituent on the 1, 3or 5 carbon on the triazine ring is a phenyl group with a hydroxyl grouportho to the point of attachment to the triazine ring. In general thisclass of materials is well known in the art.

For example, U.S. Pat. No. 3,843,371 discloses hydroxyphenyltriazinesfor use in photographic materials. The triazines in this patent,however, show poor solubilities and poor stabilities.

U.S. Pat. No. 3,896,125 discloses hydroxyphenyl triazines, but these,too are poorly soluble and discolor with time.

The use of hydroxyphenyltriazines alone or in combination with otherlight stabilizers such as hydroxyphenylbenzotriazoles, benzophenones,oxanilides, cyanoacrylates, salicylates, and hindered amine lightstabilizers (HALS), for the stabilization of polymers is also wellknown. For example, U.S. Pat. Nos. 4,853,471, 4,921,966, and 4,973,701,4,973,702 disclose such combinations.

Typically, the aforementioned aryl ring with the hydroxyl group ortho tothe point of attachment to the triazine ring is based on resorcinol and,consequently, this aryl ring also contains a second substituent (eithera hydroxyl group or a derivative thereof) para- to the point ofattachment to the triazine ring. For example, U.S. Pat. Nos. 3,118,837and 3,244,708 disclose p-alkoxy-o-hydroxyphenyl triazines with improvedUV protection, but many embodiments of such triazines exhibit poorcompatibility and solubility, and poor yellowing performance.

This para-substituent can be “non-reactive,” as in the case of analkyloxy group, or “reactive” as in the case of a hydroxyalkyloxy(active hydrogen reactive site) or (meth)acryloyl (ethylenicunsaturation reactive site) group. For the purposes of the presentinvention, the former are referred to as “non-bondable”benzocycle-substituted pyrimidines and triazines and the latter arereferred to as “bondable” benzocycle-substituted pyrimidines andtriazines.

Low volatility is an important characteristic of stabilizers used in anyapplications where high temperatures are encountered. High temperaturesare used in the processing of thermoplastics and in the curing ofthermoset resins and coatings. High temperatures are also often presentin the end-use applications for the stabilized material. Low volatilitywill prevent loss of the stabilizer during processing, curing, and hightemperature end-uses. Besides reducing losses of stabilizer duringprocessing or curing, low volatility will minimize processing problemssuch as die lip build-up and plate-out.

Many polymer additives (such as ultraviolet light stabilizers) migrateout of the polymer substrate to be protected, or are adsorbed(chemically or physically) by one or more systems components (such aspigments), thereby diminishing their effectiveness. Such migration andadsorption problems are examples of the general problems of lack ofsolubility and compatibility found for many commercial polymeradditives.

Bondable triazines are well known in the art. For example, U.S. Pat.Nos. 3,423,360, 4,962,142 and 5,189,084 disclose various bondable andthe incorporation of these compounds into polymers by chemical bonding.Bondable stabilizers have a potential advantage in this respect in that,depending on the bondable functionality and the particular polymersystem to be stabilized, they can be chemically incorporated into apolymer structure via reaction of the bondable functionality eitherduring polymer formation (such as in the case of polymerizing monomersor a crosslinking polymer system) or subsequently with a preformedpolymer having appropriate reactive functionality. Accordingly, due tosuch bonding, migration of these UV absorbers between layers ofmulti-layer coatings and into polymer substrates is greatly reduced.

SUMMARY OF THE INVENTION

The present invention provides a new class of benzocycle-substitutedpyrimidines and triazines depicted below, in which a substituentattached to the triazine or pyrimidine ring is a fused benzocyclicgroup:

wherein X signifies hydrogen or a blocking group, A can be a nitrogen oroptionally substituted methine, and the fused ring designated by S is anon-aromatic 4 to 12 membered ring, optionally containing one or moreheteroatoms; any of the three rings may bear one or more additionalsubstituents. These fused benzocyclic-substituted triazines andpyrimidines have the advantage of being highly soluble in andcompatible; of having extremely low volatility, and therefore low lossesduring high temperature processing or curing; of being highly effectivein inhibiting yellowing; and of being highly effective in preventingdegradation of polymers and coatings due to the action of actinicradiation, heat, oxygen, and moisture.

The benzocyclic substituted triazine and pyrimidine UV absorbers of thepresent invention possess exceptionally low volatility, lower than mostcurrent art UV absorbers. Furthermore these benzocyclic triazine UVabsorbers, impart improved weatherability and yellowing resistance topolymers compared to current art UV absorbers. None of the previouslyavailable triazine UV stabilizers and absorbers combine the unexpectedlow volatility along with the weatherability, yellowing resistance,solubility, and compatibility of the benzocyclic substituted triazineand pyrimidine absorbers and stabilizers of the present invention.

More specifically, the new benzocycle-substituted pyrimidines andtriazines of the present invention have general formula (I):

wherein

each A is independently nitrogen or methine optionally substituted withR², and at least two A are nitrogen;

each of T and T′ is independently a direct bond, carbon, oxygen,nitrogen, sulfur, phosphorous, boron, silicon, or functional groupscontaining these elements;

X is independently selected from hydrogen and a blocking group;

each of R¹ and R² is independently a hydrocarbyl group, a functionalhydrocarbyl group, hydroxy, alkoxy, hydrogen, halogen, cyano, orisocyano;

each of Y, Z, R³ and R⁴ are independently a hydrogen, hydrocarbyl group,a functional hydrocarbyl group, halogen, hydroxyl, cyano,—O(hydrocarbyl), —O(functional hydrocarbyl),—N(hydrocarbyl)(hydrocarbyl), —N(functional hydrocarbyl)(functionalhydrocarbyl), —N(hydrocarbyl)(functional hydrocarbyl), —S(hydrocarbyl),—S(functional hydrocarbyl), —SO₂(hydrocarbyl), —SO₂(hydrocarbyl),—SO₃(hydrocarbyl), —SO₃(functional hydrocarbyl), —COO(hydrocarbyl),—COO(functional hydrocarbyl), —CO(hydrocarbyl), —CO(functionalhydrocarbyl, —OCO(hydrocarbyl), —OCO(functional hydrocarbyl),—N(hydrocarbyl)(hydrocarbyl), —CONH₂, —CONH(hyrdocarbyl),—CONH(functional hyrdocarbyl), —CON(hydrocarbyl)(hyrdocarbyl),—CON(hydrocarbyl)(functional hyrdocarbyl), —CON(functionalhydrocarbyl)(functional hyrdocarbyl), —S(functional hydrocarbyl),—SO₂(functional hydrocarbyl), —SO₃(functional hydrocarbyl),—COO(functional hydrocarbyl), —CO(functional hydrocarbyl),—OCO(functional hydrocarbyl), or a hydrocarbyl group substituted by anyof the above groups;

each G is independently a direct bond, nitrogen, sulfur, oxygen,phosphorous, boron, silicon, selenium, tellurium, or functional groupscontaining these elements;

each of m, n, and o is independently an integer between 0 and 4,provided that when both G are direct bonds, the sum of m, n and o isbetween 2 and 10, and that when one G is a direct bond, the sum of m, nand o is between 1 and 9, and when neither G is a direct bond, the sumof m, n and o is between 0 and 8;

p is an integer between 0 and 3; and

q is an integer between 0 and 20.

Preferably, T′ is an oxygen atom and Y is a group L, to give amono-resorcinol derived benzocycle-substituted pyrimidine or triazine offormula (II):

wherein

L is defined as Y, Z, R³ and R⁴ as defined above; and

substituents A, G, T, X, Y, Z, R¹ to R⁴, and subscripts m, n, o, p, andq, are defined as above for general formula (I).

More preferably, TZ in formula (II) is a resorcinol derivative offormula (IIIa) or (IIIb):

to give a mono benzocycle bis-resorcinol derived triazine of formulas(IVa) and (IVb):

More Preferably, each L in formulas III and IV are independentlyselected from the group consisting of:

hydrogen;

an alkyl of 1 to 24 carbon atoms optionally substituted by one or morehydroxy, alkoxy, carboxy, carboalkoxy, amino, amido, carbamato, or epoxygroups, and which may contain one or more carbonyl groups, oxygen atomsor nitrogen atoms in the chain;

an alkenyl of 2 to 24 carbon atoms optionally substituted by one or morehydroxy, alkoxy, carboxy, carboalkoxy, amino, amido, carbamato, or epoxygroups, and which may contain one or more carbonyl groups, oxygen atomsor nitrogen atoms in the chain;

an aralkyl of 7 to 24 carbon atoms optionally substituted by one or morehydroxy, alkoxy, chloro, cyano, carboxy, carboalkoxy, amino, amido,carbamato, or epoxy groups, and which may contain one or more carbonylgroups, oxygen atoms or nitrogen atoms in the chain;

a polyoxyalkylene radical of the formula XII

—CH₂—CH(OH)—CH₂—O—(CH₂—(CH₂)_(u)—O—)_(mm)—D₁  (XII)

wherein D₁ is hydrogen, —CH₂—CH(OH)—CH₂—OH

 or R²⁵;

a polyoxyalkylene radical of the formula XIII

—CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—D₂  (XIII)

wherein D₂ is —(CH₂)_(u)—CO—R²² or R²⁵;

a polyoxyalkylene radical of the formula VIII

—YY—O—CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—D₃  (XIV)

wherein D₃ is —(CH₂)_(u)—CO—R²² or R²⁵;

a polyoxyalkylene radical of the formula XV

—(CH₂)_(kk)—CH(R²¹)—CO—B₁—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—B₁—D₄  (XV)

wherein D₄ is hydrogen of R²⁵;

a polyoxyalkylene radical of the formula XVI

—CO—CH₂—CH₂—NH—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—D₅  (XVI)

wherein D₅ is —NH₂, —NH—(CH₂)₂—COO—R²³ or —O—R²⁵;

a polyoxyalkylene radical of the formula XVII

—YY—O—CO—CH₂—CH₂—NH—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—D₅  (XVII)

wherein D₅ is as defined under formula (XVI);

a polyoxyalkylene radical of the formula XVIII

—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—D₆  (XVIII)

wherein D₆ is —NH—CO—R²⁴, —OR²⁵, OH or H;

a polyoxyalkylene radical of the formula XIX

 wherein

D₇ is —OR²⁵, —NHCOR²⁴ or —OCH₂CH₂OR²⁵;

R²¹ is hydrogen or C₁-C₁₆ alkyl;

R²² is halogen or —O—R²³;

R²³ is hydrogen, C₁-C₆ alkyl, C₃-C₆ alkenyl, aryl, or aryl-C₁-C₄-alkyl;

R²⁴ is hydrogen, C₁-C₁₂ alkyl or aryl;

R²⁵ is C₁-C₁₆ alkyl, C₅-C₁₂ cycloalkyl, C₃-C₆ alkenyl, C₁-C₁₂ alkylarylor aryl-C₁-C₄ alkyl;

R²⁶ is hydrogen or C₁-C₄ alkyl;

R²⁷ is hydrogen, C₁-C₁₈ alkyl, C₃-C₆ alkenyl, C₁-C₁₈ alkoxy, halogen oraryl-C₁-C₄-alkyl;

R²⁸ and R²⁹ independently of one another are hydrogen, C₁-C₁₈ alkyl,C₃-C₆ alkenyl, C₁-C₁₈ alkoxy, or halogen;

R³⁰ is hydrogen, C₁-C₄ alkyl or CN;

YY is unsubstituted or substituted C₂-C₂₀ alkyl;

kk is zero or an integer from 1-16;

B₁ is O or NH;

mm is an integer from 2 to 60;

nn is an integer from 2 to 6;

u is an integer from 1 to 4.

Preferred in the present invention are compounds of formula (IV) whereinboth G are direct bonds, m=4, n, o, p and q are 0, and all A arenitrogen of formula (IVc):

Even more preferred in the present invention arebis-benzocycle-substituted pyrimidines and triazines of formula (V):

wherein all substituents are as defined above for general formulas (I)to (IV).

Most preferred in the present invention are compounds of formula 5wherein all G are direct bonds; m=4; n, o, p, and q are 0; and all A arenitrogen, said compound having formula:

wherein

L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or afunctional hydrocarbyl group of 1 to 24 carbon atoms;

X is independently selected from hydrogen and a blocking group; and

R³ and R⁴ are independently hydrogen, hydrocarbyl, functionalhydrocarbyl, halogen, hydroxyl, —O(hydrocarbyl), —O(functionalhydrocarbyl), —S(hydrocarbyl), —SO₂(hydrocarbyl), —SO₃(hydrocarbyl),—COO(hydrocarbyl), —CO(hydrocarbyl), —OCO(hydrocarbyl),—N(hydrocarbyl)(hydrocarbyl), —S(functional hydrocarbyl),—SO₂(functional hydrocarbyl), —SO₃(functional hydrocarbyl),—COO(functional hydrocarbyl), —CO(functional hydrocarbyl),—OCO(functional hydrocarbyl), —N(functional hydrocarbyl)(functionalhydrocarbyl) or cyano.

The benzocycle-substituted pyrimidines and triazines of the presentinvention further comprise oligomeric species of formulas (VI) and(VII):

wherein

A, T, T′, Y, Z, R¹-R⁴, G, m-q, and X, are as defined above;

r is an integer between 2 and 4;

D when r is 2, is selected from the group consisting of C₂-C₁₆ alkyl,C₄-C₁₂ alkenyl, xylylene, C₃-C₂₀ alkyl which is interrupted by one ormore oxygen atoms, hydroxy-substituted C₃-C₂₀ alkyl which is interruptedby one or more oxygen atoms, —CH₂CH(OH)CH₂O—R¹⁵—OCH₂CH(OH)CH₂,—CO—R¹⁶—CO—, —CO—NH—R¹⁷—NH—CO—, —(CH₂)_(s)—COO—R¹⁸—OCO—(CH₂)_(s)—apolyoxyalkylene bridge member of the formula XX

—C₂—CH(OH)—CH₂—O—(CH₂—(CH₂)_(u)—O—)_(mm)—CH₂—CH(OH)—CH₂—  (XX),

 a polyoxyalkylene bridge member of the formula XXI

—CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—(CH₂)_(u)—CO—  (XXI),

 a polyoxyalkylene bridge member of the formula XXII

—YY—O—CO(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—(CH₂)_(u)—COO—YY—  (XXII),

 a polyoxyalkylene bridge member of the formula XXIII

—(CH₂)_(kk)—CH(R²¹)—CO—B_(1\)—(C_(nn)H_(2nn)—O—)_(mm)C_(nn)H_(2nn)—B₁—CO—CH(R²¹)—(CH₂)_(kk)—  (XXIII),

 a polyoxyalkylene bridge member of the formula XXIV

 a polyoxyalkylene bridge member of the formula XXV

—YY—O—CO—(CH₂)₂—NH—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—NH—(CH₂)₂COO—YY—  (XXV),

 a polyoxyalkylene bridge member of the formula XXVI

—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—  (XXVI),

 and a polyoxyalkylene bridge member of the formula XXVII

—CH(CH₃)—CH₂—(O—CH(CH₃)—CH₂)_(a)—(O—CH₂—CH₂)_(b)—(O—CH₂—CH(CH₃)_(c)—  (XXVII),

 wherein

a+c=2.5 and b=8.5 to 40.5 or a+c=2 to 33 and b=0,

R²¹ is hydrogen or C₁-C₁₆ alkyl,

R²² is halogen or —O—R²³,

R²³ is hydrogen, C₁-C₆ alkyl, C₃-C₆ alkenyl, aryl, or aryl- C₁-C₄-alkyl,

R²⁴ is hydrogen, C₁-C₁₂ alkyl or aryl,

R²⁵ is C₁-C₁₆ alkyl, C₅-C₁₂ cycloalkyl, C₃-C₆ alkenyl, C₁-C₁₂ alkylarylor aryl-C₁-C₄ alkyl,

R²⁶ is hydrogen or C₁-C₄ alkyl,

R²⁷ is hydrogen, C₁-C₁₈, alkyl, C₃-C₆ alkenyl, C₁-C₁₈ alkoxy, halogen oraryl-C₁-C₄ alkyl,

R²⁸ and R²⁹ independently of one another are hydrogen, C₁-C₁₈ alkyl,C₃-C₆ alkenyl, or C₁-C₁₈ alkoxy, or halogen;

R³⁰ is hydrogen, C₁-C₄ alkyl or CN,

YY is unsubstituted or substituted C₂-C₂₀ alkyl,

kk is zero or an integer from 1-16,

B₁ is O or NH,

mm is an integer from 2 to 60,

nn is an integer from 2 to 6,

u is an integer from 1 to 4;

when r is 3, D is

and when r is 4, D is

 wherein

R¹⁹ is C₃-C₁₀ alkanetriyl and R²⁰ is C₄-C₁₀ alkanetetryl; and s is 1-6;

R¹⁵ is C₂-C₁₀ alkyl, C₂-C₁₀ oxaalkyl or C₂-C₁₀ dithiaalkyl, phenyl,naphthyl, diphenyl, or C₂-C₆ alkenyl, or phenylene-XX-phenylene whereinXX is —O—, —S—, —SO₂—, —CH₂—, or —C(CH₃)₂—;

R¹⁶ is C₂-C₁₀ alkyl, C₂-C₁₀ oxaalkyl or C₂-C₁₀ dithiaalkyl, phenyl,naphthyl, diphenyl, or C₂-C₆ alkenyl provided that when r is 3 thealkenyl has at least 3 carbons;

R¹⁷ is C₂-C₁₀ alkyl, phenyl, naphthyl, diphenyl, or C₂-C₆ alkenyl,methylenediphenylene, or C₄-C₁₅ alkylphenyl; and

R¹⁸ is C₂-C₁₀ alkyl, or C₄-C₂₀ alkyl interrupted by one or more oxygenatoms; and

wherein A, T, T′, Y, Z, R¹-R⁴, G, m-q, and X, are as defined above; r is2 or 3; X′, when r is 2, is —CO—R¹⁶—CO—, —CO₂—R¹⁶—CO₂—, —SO₂—R¹⁶—SO₂—,—CO—NH—R¹⁷—NH—CO—, a polyoxyalkylene bridge member of formula—CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—(CH₂)_(u)—CO—, or

when r=3, X′ is:

—(—CO₂—R¹⁶)R¹⁹, —(—CONH—R¹⁶)R¹⁹, —(—SO₂—R¹⁶)R¹⁹

wherein R¹⁶, R¹⁷, R¹⁸, and R¹⁹ are as defined above.

The benzocycle-substituted pyrimidines and triazines of the presentinvention also comprise oligomeric species of the formulas (VIII) and(IX):

wherein A, T, T′, Y, Z, R¹ through R³, G, m through q, and X, are asdefined above;

R⁴ is selected from the group consisting of straight chain alkyl of 1 to12 carbon atoms, branched chain alkyl of 1 to 12 carbon atoms,cycloalkyl of 5 to 12 carbon atoms, alkyl substituted by cyclohexyl,alkyl interrupted by cyclohexyl, alkyl substituted by phenylene, alkylinterrupted by phenylene, benzylidene, —S—, —S—S—, —S—E—S—, —SO—, —SO₂—,—SO—E—SO—, —SO₂—E—SO₂—, —CH₂—NH—E—NH—CH₂—, and

wherein E is selected from the group consisting of alkyl of 2 to 12carbon atoms, cycloalkyl of 5 to 12 carbon atoms, alkyl interrupted bycyclohexyl of 8 to 12 carbon atoms, alkyl terminated by cyclohexyl of 8to 12 carbon atoms; and

r is an integer between 2 and 4;

 wherein

each A is independently nitrogen or methine optionally substituted withR², and at least two A are nitrogen;

each of T and T′ is independently a direct bond, carbon, oxygen,nitrogen, sulfur, phosphorous, boron, silicon, or a functional groupcontaining these elements;

each of Y, Z, R¹, and R² is independently a hydrocarbyl group, afunctional hydrocarbyl group, hydrogen, halogen, cyano, or isocyano;

each G is independently a direct bond, nitrogen, sulfur, oxygen,phosphorous, boron, silicon, selenium, tellurium, or functional groupscontaining these elements;

each of m, n, and o is independently an integer between 0 and 4,provided that when both G are direct bonds, the sum of m, n and o isbetween 2 and 10, and that when one G is a direct bond, the sum of m, nand o is between 1 and 9, and when neither G is a direct bond, the sumof m, n and o is between 0 and 8;

p is an integer between 0 and 3;

q is an integer between 0 and 12;

X is independently hydrogen or a blocking group;

R³ and R⁴ are independently hydrogen, hydrocarbyl, functionalhydrocarbyl, halogen, hydroxyl, —O(hydrocarbyl), —O(functionalhydrocarbyl), —S(hydrocarbyl), —SO₂(hydrocarbyl), —SO₃(hydrocarbyl),—COO(hydrocarbyl), —CO(hydrocarbyl), —OCO(hydrocarbyl),—N(hydrocarbyl)(hydrocarbyl), —S(functional hydrocarbyl),—SO₂(functional hydrocarbyl), —SO₃(functional hydrocarbyl),—COO(functional hydrocarbyl), —CO(functional hydrocarbyl),—OCO(functional hydrocarbyl), —N(functional hydrocarbyl)(functionalhydrocarbyl) or cyano;

r is an integer between 2 and 4;

D, when r is 2, is selected from the group consisting of C₂-C₁₆alkylene,C₄-C₁₂alkenylene, xylylene, C₃-C₂₀alkylene which is interrupted by oneor more oxygen atoms, hydroxy-substituted C₃-C₂₀alkylene which isinterrupted by one or more oxygen atoms, —OOCR14COO—,—CH₂CH(OH)CH₂O—R¹⁵—OCH₂CH(OH)CH₂, —CO—R¹⁶—CO—, —CO—NH—R¹⁷—NH—CO—, and—(CH₂)_(s), —COO—R¹⁸—OCO—(CH₂)_(s)—; and

 when r is 3, D is

 and when r is 4, D is

 wherein

R¹⁹ is C₃-C₁₀alkanetriyl and R²⁰ is C₄-C₁₀alkanetetryl;

s is 1-6;

r is an integer between 2 and 4;

D, when r is 2, is selected from the group consisting of C₂-C₁₆alkylene,C₄-C₁₂alkenylene, xylylene, C₃-C₂₀alkylene which is interrupted by oneor more oxygen atoms, hydroxy-substituted C₃-C₂₀alkylene which isinterrupted by one or more oxygen atoms,—CH₂CH(OH)CH₂O—R¹⁵—OCH₂CH(OH)CH₂, —CO—R¹⁶—CO—, —CO—NH—R¹⁷—NH—CO—, and—(CH₂)—COO—R¹⁸—OCO—(CH₂)_(s)—; and

 when r is 3, D is

 and when r is 4, D is

 wherein

R¹⁹ is C₃-C₁₀alkanetriyl and R²⁰ is C₄-C₁₀alkanetetryl;

s is 1-6;

R⁸ is C₁-C₁₈ alkyl, C₃-C₁₈ alkenyl, C₃-C₂₀ alkyl, which is interruptedby O, N, or S, and/or substituted by OH, C₁-C₄ alkyl which issubstituted by —P(O)(OR¹⁴)₂, —N(R⁹)(R¹⁰), or —OCOR¹¹, and/or OH, or isglycidyl, cyclohexyl or C₇-C₁₁ phenylalkyl;

R⁹ and R¹⁰ are each independently of the other, C₁-C₁₂ alkyl, C₃-C₁₂alkoxyalkyl, C₄-C₁₆ dialkylaminoalkyl or C₅-C₁₂ cycloalkyl, or R⁹ andR¹⁰, when taken together, are C₃-C₉ alkylene or C₃-C₉ oxaalkylene ofC₃-C₉ azaalkylene;

R¹¹ is C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl or phenyl;

R¹² is C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl, phenyl, C₁-C₁₂ alkoxy, phenoxy,C₁-C₁₂ alkylamino; phenylamino, tolylamino or naphthylamino;

R¹³ is C₁-C₁₂ alkyl, phenyl, naphthyl or C₇-C₁₄ alkylphenyl;

R¹⁴ is C₁-C₁₂ alkyl or phenyl;

R¹⁵ is C₂-C₁₀ alkylene phenylene or a phenylene-x-phenylene-group,wherein X is —O—, —S—, —SO₂—, —CH₂—, or —C(CH₃)₂—;

R¹⁶ is C₂-C₁₀ alkylene, C₂-C₁₀ oxaalkylene or C₂-C₁₀ dithiaalkylene,phenylene, naphthylene, diphenylene or C₂-C₆ alkenylene;

R¹⁷ is C₂-C₁₀ alkylene, phenylene, naphthylene, methylenediphenylene orC₇-C₁₅ alkylphenylene, and

R¹⁸ is C₂-C₁₀ alkylene or C₄-C₂₀ alkylene which is interrupted by one ormore oxygen atoms.

The benzocycle-substituted pyrimidines and triazines of the presentinvention may optionally have the added benefit of being capable ofbeing chemically bonded to appropriate polymer systems via functionalityattached to the benzocycle, pyrimidine and triazine groups (e.g., by ahydroxyl, ethylenic unsaturated and/or activated unsaturated group inone or more of R¹, R², Y or Z).

These benzocycle-substituted pyrimidines and triazines may in general beprepared via a number of procedures well known in the art, for example,those described in Brunetti, H; Luethi, C.; Helv. Chemica Acta, 55(1972) pp. 1566-1595; Tanimoto, S.; Yamagata, M. Senryo to Yakahin, 40(1995) pp 339ff; U.S. Pat. Nos. 5,106,972, 5,288,868, 5,438,138, and5,478,935; EP 395,938; EP 577,559; EP 649,841; EP 779,280; WO 9,628,431;GB 884,802; and Japanese Patent Kokai Tokkyo Koho 9,059,263 all of whichare incorporated herein by reference for all purposes as if fully setforth.

The novel benzocycle-substituted pyrimidines and triazines of thepresent invention are particularly useful as ultraviolet light absorberagents for stabilizing a wide variety of materials including, forexample, organic compounds, oils, fats, waxes, cosmetics, dyes andbiocides, and particularly various organic polymers (both crosslinkedand non-crosslinked) used in applications such as photographicmaterials, plastics, fibers or dyed fibers, rubbers, paints and othercoatings, and adhesives. The present invention, consequently, alsorelates to (1) a method of stabilizing a material which is subject todegradation by actinic radiation (e.g., an organic material such as anorganic polymer in the form of a film, fiber, shaped article or coating)by incorporating into said material an amount of an actinic radiationstabilizer composition effective to stabilize the material against theeffects of actinic radiation, wherein the actinic radiation stabilizercomposition comprises the inventive benzocycle-substituted1,3,5-triazine or pyrimidine; and (2) the material so stabilized.

The novel benzocycle-substituted pyrimidines and triazines of thepresent invention are also effective as ultraviolet light screeningagents in applications such as sunscreens and other cosmeticpreparations, capstock layers for extruded polymers, dyed fibers andlaminated UV-screening window films, among others. The presentinvention, consequently, also relates (1) to a method of protecting asubstrate against degradation by actinic radiation by applying to thesubstrate an actinic radiation screening layer (e.g., a coating film orcapstock layer) containing an actinic radiation screening composition inan amount effective to reduce the amount of actinic radiation impingingon the substrate, wherein the actinic radiation screening compositioncomprises the inventive benzocycle-substituted pyrimidines andtriazines; and (2) the substrate so protected.

The novel benzocycle-substituted pyrimidines and triazines of thepresent invention may also be employed to form light stabilizingcompositions. Such light stabilizing compositions may include a varietyof other components known in the art including other ultraviolet lightabsorbers of the triazine class, other ultraviolet light absorbers ofdifferent classes (e.g. benzotriazoles, benzophenones), hindered aminelight stabilizers, radical scavengers, antioxidants and the like.

These and other features and advantages of the present invention will bemore readily understood by those of ordinary skill in the art from areading of the following detailed description.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

The Benzocycle-substituted Pyrimidines and Triazines

As used herein, the term “benzocycle-substituted pyrimidines andtriazines” broadly refers to any compound of formulas (I) through (IX),above.

As used herein, the term “benzocycle” broadly refers to any compound orsubstituent of general formula (X):

Wherein substituents G, R¹, R², and subscripts m, n, o, p, and q, aredefined as above for general formulas (I), (II), (III), and (IV);

The term “hydrocarbyl” in the context of the present invention, and inthe above formulas, broadly refers to a monovalent hydrocarbon group inwhich the valency is derived by abstraction of a hydrogen from a carbonatom. Hydrocarbyl includes, for example, aliphatics (straight andbranched chain), cycloaliphatics, aromatics and mixed character groups(e.g., aralkyl and alkaryl). Hydrocarbyl also includes such groups withinternal unsaturation and activated unsaturation. More specifically,hydrocarbyl includes (but is not limited to) such groups as alkyl,cycloalkyl, aryl, aralkyl, alkaryl, alkenyl, cycloalkenyl and alkynyl,preferably having up to 24 carbon atoms. A hydrocarbyl may optionallycontain a carbonyl group or groups (which is/are included in the carboncount) and/or a heteroatom or heteroatoms (such as at least one oxygen,sulfur, nitrogen or silicon), in the chain or ring.

The term “functional hydrocarbyl” in the context of the presentinvention, and in the above formulas, broadly refers to a hydrocarbylpossessing pendant and/or terminal reactive and/or latent reactivefunctionality and/or leaving groups. “Reactive” functionality refers tofunctionality which is reactive with common monomer/polymerfunctionality under normal conditions well understood by those personsof ordinary skill in the relevant art. As non-limiting examples ofreactive functionality may be mentioned active hydrogen-containinggroups such as hydroxyl, amino, carboxyl, thio, amido, carbamoyl andactivated methylene; isocyanato; cyano; epoxy; ethylenically unsaturatedgroups such as allyl and methallyl; and activated unsaturated groupssuch acryloyl and methacryloyl, and maleate and maleimido (including theDiels-Alder adducts thereof with dienes such as butadiene). “Latentreactive” functionality within the meaning of the present invention and,as would clearly be understood by those persons of ordinary skill in theart, refers to reactive functionality which is blocked or masked toprevent premature reaction. As examples of latent reactive functionalitymay be mentioned ketimines and aldimines (amines blocked, respectively,with ketones and aldehydes); amine-carboxylate salts; and blockedisocyanates such as alcohol (carbamates), oxime and caprolactam blockedvariations. A “leaving” group within the meaning of the presentinvention, as would clearly be understood by those persons of ordinaryskill in the relevant art, is a substituent attached to the hydrocarbylchain or ring which during reaction is dislodged or displaced to createa valency on a carbon or heteroatom in the hydrocarbyl chain or ring,said valency being filled by a nucleophile. As examples of leavinggroups may be mentioned halogen atoms such as chlorine, bromine andiodine; hydroxyl groups (protonated and unprotonated); quaternaryammonium salts (NT₄ ⁺); sulfonium salts (ST₃ ⁺); and sulfonates(—OSO₃T); where T is, e.g., methyl or para-tolyl. Of all these classesof reactive functionality, the preferred functionality includeshydroxyl, —COOR⁵, —CR⁶═CH₂, —CO—CR⁶═CH₂, Cl, an isocyanate group, ablocked isocyanate group and —NHR⁵, wherein

R⁵ is selected from hydrogen and a hydrocarbyl (preferably of up to 24carbon atoms); and

R⁶ is selected from hydrogen and an alkyl of 1 to 4 carbon atoms(preferably hydrogen and methyl).

The term “hydrocarbylene” in the context of the present invention is adivalent hydrocarbon group in which both valencies derive by abstractionof hydrogens from carbon atoms. Included within the definition ofhydrocarbylene are the same groups as indicated above for hydrocarbyland functional hydrocarbyl with, of course, the extra valency (forexample, alkylene, alkenylene, arylene, alkylaryl, etc.).

The term “functional hydrocarbylene” in the context of the presentinvention refers to a species of hydrocarbylene possessing pendantreactive functionality, latent reactive functionality and/or leavinggroups. The term “non-functional hydrocarbylene” in the context of thepresent invention refers generally to a hydrocarbylene other than afunctional hydrocarbylene.

The benzocycle-substituted pyrimidines and triazines in accordance withthe present invention also relate to latent stabilizing compoundsagainst actinic radiation of the general formulas (I), (III), and (IV),wherein at least one of the hydroxyl groups on an aryl ring ortho to thepoint of attachment to the triazine or pyrimidine ring is blocked, thatis, wherein at least one X is other than hydrogen. Such latentstabilizing compounds liberate the effective stabilizers by cleavage ofthe O—X bond, e.g., by heating or by exposure to UV radiation. Latentstabilizing compounds are desirable because they have many favorableproperties, i.e., good substrate compatibility, good color properties, ahigh cleavage rate of the O—X bond and a long shelf life. The use oflatent stabilizing compounds is further described in U.S. Pat. Nos.4,775,707, 5,030,731, 5,563,224 and 5,597,854, which are incorporatedherein for all purposes as if fully set forth.

Latent stabilizing compounds comprising the benzocycle-substitutedpyrimidines and triazines in accordance with the present invention canbe prepared from compounds of the general formulas (I), (II) and (IV)through (IX), wherein at least one X is hydrogen, by subjecting saidcompounds to a further reaction to form latent stabilizing compounds, asdescribed in the immediately preceding incorporated references.

As preferred examples of blocking groups X may be mentioned one or moreof the following groups: allyl, —COR^(a), —SO₂R^(b), —SiR^(c)R^(d)R^(e),—PR^(f)R^(g) or —POR^(f)R^(g), —CONHR^(h), wherein

each R^(a) is independently selected from C₁-C₈ alkyl,halogen-substituted C₁-C₈ alkyl, C₅-C₁₂ cycloalkyl, C₂-C₈ alkenyl,—CH₂—CO—CH₃, C₁-C₁₂ alkoxy, and phenyl or phenoxy which is unsubstitutedor substituted by C₁-C₁₂ alkyl, C₁-C₄ alkoxy, halogen and/or benzyl;

each R^(b) is independently selected from C₁-C₁₂ alkyl, C₆-C₁₀ aryl andC₇-C₁₈ alkylaryl;

each R^(c), R^(d) and R^(e) is independently selected from C₁-C₁₈ alkyl,cyclohexyl, phenyl and C₁-C₁₈ alkoxy;

each R^(f) and R^(g) is independently selected from C₁-C₁₂ alkoxy,C₁-C₁₂ alkyl, C₅-C₁₂ cycloalkyl, and phenyl or phenoxy which isunsubstituted or substituted by C₁-C₁₂ alkyl, C₁-C₄ alkoxy, halogenand/or benzyl; and

each R^(h) is independently selected from C₁-C₈ alkyl, C₅-C₁₂cycloalkyl, C₂-C₈ alkenyl, —CH₂—CO—CH₃, and phenyl which isunsubstituted or substituted by C₁-C₁₂ alkyl, C₂-C₈ alkenyl, C₁-C₄alkoxy, halogen and/or benzyl.

The reaction to give the latent stabilizing compounds of the presentinvention of the general formula (I), (III), and (IV), in which X isallyl, —COR^(a), —SO₂R^(b), —SiR^(c)R^(d)R^(e), —PR^(f)R^(g) or—POR^(f)R^(g), can be carried out, for example, by reaction of thecompounds of the general formula (III) through (X), wherein at least oneX is hydrogen with the corresponding halides such as allyl chloride,Cl—COR^(a), Cl—SO₂R^(b), Cl—SiR^(c)R^(d)R^(e), Cl—PR^(f)R^(g),orCl—POR^(f)R^(g). The reaction to give the latent stabilizing compoundsof the present invention of the general formulas (III) through (X) inwhich X is —CONHR^(h) can be carried out, for example, by reaction ofthe compounds of the general formulas (III) through (X), wherein atleast one X is hydrogen with the corresponding isocyanates. Furthermore,acylated compounds can be obtained by reaction with anhydrides, ketenesor esters, such as lower alkyl esters, as is well known to one skilledin the art. The above-described reagents may be used in approximatelyequimolar amounts or in excess, for example, from 2 to 20 mol withrespect to the hydroxyl groups desired to be made latent in the startingcompound of the general formula (I), (III), or (IV).

Catalysts customarily used for acylation, sulfonylation,phosphonylation, silylation or urethanation reactions may be used informing the latent stabilizing benzocycle-substituted pyrimidines andtriazines of the present invention. For example, acylation andsulfonylation reaction catalysts such as tertiary or quaternary amines,such as triethylamine, dimethylaminopyridine or tetrabutylammoniumsalts, may be used for forming these latent stabilizing compounds.

The reaction may be carried out in the presence of a solvent, such asrelatively inert organics, e.g., hydrocarbons such as toluene andxylene, chlorinated hydrocarbons such as carbon tetrachloride orchloroform, or ethers such as tetrahydrofuran or dibutyl ether, orwithout a solvent. Alternatively, the reagent(s) may be employed as thesolvent. The reaction temperature is usually between room temperatureand about 150° C., for example, up to the boiling point of the solventwhen a solvent is used.

In preferred embodiments, each X is hydrogen.

In preferred embodiments

L is selected from the group consisting of hydrogen, C₁-C₂₄ alkyl ormixtures thereof; C₁-C₂₄ branched alkyl or mixtures thereof; C₃-C₆alkenyl; —COR¹²; —COOR¹²; —CONHR¹²; —SO₂R¹³; C₁-C₁₈ alkyl which issubstituted with one or more of the groups: hydroxy, C₁-C₁₈ alkoxy,C₃-C₁₈ alkenoxy, halogen, phenoxy, C₁-C₁₈ alkyl-substituted phenoxy,C₁-C₁₈ alkoxy-substituted phenoxy, halogen-substituted phenoxy, —COOH,—COOR⁸, —CONH₂, —CONHR⁹, —CON(R⁹)(R¹⁰), —NH₂, —NHR⁹, —N(R⁹)(R¹⁰),—NHCOR¹¹, —N(R⁹)COR¹¹, —NHCOOR¹¹, —N(R⁹)COOR¹¹, —CN, —OCOR¹¹,—OC(O)NHR⁹, —OC(O)NHR⁹, —OC(O)N(R⁹)(R¹⁰); C₂-C₅₀ alkyl which isinterrupted by one or more oxygen atoms or carbonyl groups andoptionally substituted by one or more substituents selected from thegroup consisting of hydroxy, C₁-C₁₂ alkoxy, and glycidyloxy; glycidyl;and cyclohexyl optionally substituted with hydroxyl or —OCOR¹¹.

R⁹ and R¹⁰ independently of one another are C₁-C₁₂ alkyl, C₃-C₁₂alkoxyalkyl, C₄-C₁₆ dialkylaminoalkyl, or C₅-C₁₂ cycloalkyl, or R⁹ andR¹⁰ taken together are C₃-C₉ alkylene or C₃-C₉ oxoaalkylene or C₃-C₉azaalkylene.

R¹¹ is C₁-C18 alkyl, C₂-C₁₈ alkenyl, or phenyl.

Some of these groups as well as others are described in U.S. Pat. Nos.5,106,891, 5,189,084, 5,356,995, 5,637,706, 5,726,309, EP 434,608, EP704,437, WO 96/28431, and GB 2,293,823 which are incorporated herein byreference for all purposes as if fully set forth.

L may also be an alkyl of 1-24 carbon atoms substituted by a hinderedamine light stabilizer (HALS) group of the general formula XI. Triazinescontaining tetramethylpiperidine groups are described in U.S. Pat. Nos.4,161,592 and 5,376,710, which are hereby incorporated by referenceherein as if fully set forth.

wherein

J is —O—, —NR³⁰—, —T—CH2)2—NR³⁰— wherein T is —O— or —S—, and R³⁰ isC₁-C₁₂ alkyl or hydrogen;

R³¹is hydrogen or C₁-C₈ alkyl;

R³² is hydrogen, oxygen, C₁-C₂₁ alkoxyalkyl, C₇-C₈ aralkyl,2,3-epoxypropyl, and aliphatic acyl group with 1-4 C atoms or one of thegroups —CH₂COOR³³, —CH₂—CH(R³⁴)—R³⁵, —COOR³⁶ or —CONHR³⁶, wherein R³³ isC₁-C₁₂ alkyl, C₃-C₆ alkenyl, phenyl, C₇-C₈ aralkyl or cyclohexyl, R³⁴ isa hydrogen, methyl or phenyl, R³⁵ is hydrogen, an aliphatic, aromatic,araliphatic or alicyclic acyl group with 1-8 C atoms, wherein thearomatic part is unsubstituted or is substituted by chlorine, C₁C₄alkyl, C₁-C₈ alkoxy or by hydroxyl, and R³⁶ is C₁-C₁₂ alkyl, cyclohexyl,phenyl or benzyl;

R³⁷ is hydrogen, —OH or one of the groups —O—CO—R³⁸ or —NR³⁶—CO—R³⁸,wherein R³⁸ is C₁-C₁₂ alkyl or phenyl; and

K is —O—(C_(mm)H_(2mm))— wherein mm is 1 to 6,

Preferred among the sterically hindered amines are members of the groupconsisting of: bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate;bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate;bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate; thecondensate ofN,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine; the condensate ofN,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5 -triazine;3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione;3-dodecyl-1-(1-acetyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione;a mixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine, and mixtures thereof.

Most preferably, each L group is independently selected from hydrogen,an alkyl of 1 to 24 carbon atoms, or mixtures thereof; an alkyl of 4 to20 carbon atoms containing one or more oxygen atoms in the chain andoptionally substituted with one or more hydroxyl groups, or mixturesthereof.

Each R¹ and R² is independently selected from hydrogen, chloro, an alkylof 1 to 8 carbon atoms, an alkyloxy of 1 to 8 carbon atoms optionallycontaining an oxygen atom in the chain, a hydroxyalkyl of 1 to 8 carbonatoms group optionally containing an oxygen atom in the chain, ahydroxyalkyloxy of 1 to 8 carbon atoms group optionally containing anoxygen atom in the chain, an acyl group of 2 to 12 carbon atoms and anacyloxy of 2 to 12 carbon atoms. Especially preferred is when each R¹and R² is independently selected from hydrogen, chloro, an alkyl of 1 to4 carbon atoms, and alkoxy of 1 to 4 carbon atoms, and particularlyhydrogen, methyl, and methoxy.

Each of R³ and R⁴ is independently selected from hydrogen, a hydrocarbylgroup of 1 to 24 carbon atoms, a hydrocarbyloxy group of 1 to 24 carbonatoms, an acyl group of 2 to 24 carbon atoms and an acyloxy group of 2to 24 carbon atoms. More preferably, each R¹ is independently selectedfrom hydrogen, an alkyl of 1 to 24 carbon atoms optionally containing anoxygen atom in the chain; an alkyloxy of 1 to 24 carbon atoms optionallycontaining an oxygen atom in the chain; an alkenyl of 2 to 24 carbonatoms optionally containing an oxygen atom in the chain; an alkenyloxyof 2 to 24 carbon atoms optionally containing an oxygen atom in thechain; an acyl group of 2 to 12 carbon atoms; an acyloxy group of 2 to12 carbon atoms; and optionally substituted benzoyl. Still morepreferably, each R¹ is independently selected from hydrogen, an alkyl of1 to 8 carbon atoms, an alkyloxy of 1 to 8 carbon atoms optionallycontaining an oxygen atom in the chain, a hydroxyalkyl of 1 to 8 carbonatoms group optionally containing an oxygen atom in the chain, ahydroxyalkyloxy of 1 to 8 carbon atoms group optionally containing anoxygen atom in the chain, an acyl group of 2 to 12 carbon atoms and anacyloxy of 2 to 12 carbon atoms. Some of these groups as well as othersare described in U.S. Pat. Nos. 5,189,084, 5,354,794, 5,543,518,5,637,706, EP 434,608, EP 704,437, and WO 96/28431, which areincorporated herein by reference for all purposes as if fully set forth.

In preferred embodiments, each of R³ and R⁴ is independently selectedfrom hydrogen, halogen, an acyl of 2 to 24 carbon atoms, benzoyl, alkylof 1 to 24 carbon atoms, an alkenyl of 2 to 24 carbon atoms, acycloalkyl of 5 to 24 carbon atoms; and an aralkyl of 7 to 24 carbonatoms.

In another preferred embodiment, R³ and R⁴ are independently methylene,alkylidene, or benzylidene substituted by a benzophenone UV absorber ora benzotriazole UV absorber. Related triazine—benzotriazole andtriazine—benzophenone hybrid UV absorbers are disclosed in U.S. Pat. No.5,585,422 which is incorporated by reference herein for all purposesfully set forth. In a related preferred embodiment, R³ and R⁴ areindependently methylene, alkylidene, or benzylidene substituted by asecond triazine UV absorber. Related triazine dimers (and oligomers) aredisclosed in U.S. Pat. No. 5,726,309 and EP 704,437 which areincorporated by reference herein for all purposes fully set forth.

Preferred benzotriazoles comprise at least one member of the groupconsisting of: 2-(2′-hydroxy-5′-methylphenyl)-benzotriazole;2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole;2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole;2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole;2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole;2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole;2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)-benzotriazole;2-(2′-hydroxy-4′-octoxyphenyl)benzotriazole;2-(3′,5′-di-tert-amyl-2′-hydroxphenyl)benzotriazole;2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)-benzotriazole; amixture of2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotiazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole and2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole;2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol];the transesterification product of 2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxphenyl]benzotriazole withpolyethylene glycol 300; [R—CH₂CH—COO(CH₂)₃]₂—whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl; andderivatives thereof. Most preferred benzotriazoles are members of thegroup consisting of:2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole;2-(3′,5′-di-tert-amyl-2′-hydroxphenyl)benzotriazole;2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)-benzotriazole;2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]benzotriazolewith polyethylene glycol 300 and mixtures thereof.

In preferred embodiments, R¹¹ is selected from hydrogen and hydrocarbylof 1 to 24 carbon atoms which may optionally be substituted by hydroxylor alkoxy of 1 to 4 carbon atoms and/or contain one or more oxygenand/or nitrogen atoms in the chain. More preferably, R¹¹ is selectedfrom hydrogen and hydrocarbyl of 1 to 24 carbon atoms which mayoptionally be substituted by hydroxyl or alkoxy of 1 to 4 carbon atoms.

In preferred embodiments, R¹² is selected from hydrogen and an alkyl of1 to 4 carbon atoms. More preferably, R¹² is selected from hydrogen anda methyl group.

In preferred embodiments, R¹³ is selected from hydrogen, a hydrocarbylgroup of 1 to 8 carbon atoms, or phenyl. More preferably, R¹³ ishydrogen or methyl.

In preferred embodiments, G is a direct bond, m and o are 0, and n is 4.

Further preferred embodiments may include any combination of theparameters mentioned above.

Methods of Preparation

The term “Lewis acid” is intended to include aluminum halides,alkylaluminum halides, boron halides, tin halides, titanium halides,lead halides, zinc halides, iron halides, gallium halides, arsenichalide, copper halides, cadmium halides, mercury halides, antimonyhalides, and the like. Preferred Lewis acids include aluminumtrichloride, aluminum tribromide, trimethylaluminum, boron trifluoride,boron trichloride, zinc dichloride, titanium tetrachloride, tindichloride, tin tetrachloride, or a mixture thereof.

As used herein, the term “acid” includes any inorganic or organic acidwith at least one acidic proton, which may or may not be dissolved in anaqueous or organic solution. The organic acids include any organiccompound that contains at least one acidic functional group includingRCO₂H, RSO₃H, RSO₂H, RSH, ROH, RPO₃H, RPO₂H, wherein R is as definedabove. Preferred protic acids include HCl, HBr, HI, HNO₃, HNO₂, H₂S,H₂SO₄, H₃PO₄, H₂CO₃, acetic acid, formic acid, propionic acid, butanoicacid, benzoic acid, phthalic acid, oxalic acid, malonic acid, succinicacid, glutaric acid, adipic acid, methanesulfonic acid, andp-toluenesulfonic acid or mixtures thereof.

As used herein, the term “step-wise” means a reaction sequence wherein aseries of reactions are conducted, the first reaction producingcompounds of Formulas (XXXII), (XXXV), or (XXXVI) and being carried outto between about 50% to about 100% completion prior to addition of acompound of Formula (XXXIII) to produce compounds of Formulas (I), (IVa/b/c), or (V). Preferably the reaction is carried out to between about70% to about 100% completion prior to addition of compound of Formula(XXXIII), and more preferably to between about 75% to about 100%completion.

As used herein, the term “continuous” means a reaction sequence notdefined as “step-wise.”

The novel benzocycle-substituted pyrimidines and triazines of thepresent invention can be prepared through the Friedel-Crafts reaction ofa benzocycle moiety (XXX) with a halogen-substituted pyrimidine ortriazine compound of Formula (XXXI) or (XXXIV). See Schemes 1, 2, and 3.

wherein Hal is bromine, chlorine, or iodine. Compound (XXX) is definedas a protonated compound of Formula (X), as defined above. In compounds(XXXI) and (XXXIV) Hal, is a halogen, preferably bromine, chlorine, oriodine, and A, T, and Z are as defined above. In compound (XXXIII) L, X,T′, Y, R³, and R⁴ are as defined above.

The relative amounts of the reactants are as follows. The amount ofcompounds (XXXI) or (XXXIV) should be in sufficient amounts to reactwith benzocyclic compounds of Formula (XXX) to produce compounds ofFormula (XXXII), (XXXV), or (XXXVI). The amount of benzocyclic compoundof Formula (XXX) is important to ensure that a sufficient amount ofbenzocyclic compounds of Formula (XXXII), (XXXV), or (XXXVI) aresynthesized without excessive amounts of undesired side products such astrisbenzocyclic triazine or trisbenzocyclic pyrimidine. Moreover, excessamounts of benzocyclic compounds can lead to undesired productdistributions enriched in mono- and tris-benzocyclic triazines, or mono-and tris-benzocyclic pyrimidines thus, making product separation andpurification difficult and resource consuming.

The amount of benzocyclic compounds (XXX) should be in sufficientamounts to synthesize 2-halo-4,6-bisbenzocyclic-1,3,5-triazine,2,4-dihalo-6-benzocyclic-1,3,5-triazine,2-halo-4,6-bisbenzocyclicpyrimidine, 2,4-dihalo-6-benzocyclicpyrimidineor convert 2-halo-4,6-bisbenzocyclic-1,3,5-triazine into2,4,6-trisbenzocyclic-1,3,5-triazine or convert2-halo-4,6-bisbenzocyclicpyrimidine into2,4,6-trisbenzocyclicpyrimidine. Preferably, there should be betweenabout 1 to about 5 mol equivalents of benzocyclic compound of Formula(XXX) to compound of Formula (XXXI) or (XXXIV). The amount of aromaticcompound of Formula (XXXIII) should be between about 0.5 to about 2.5mol equivalents of aromatic compound of Formula (XXXIII) to compounds ofFormula (XXXII), (XXXV), or (XXXVI).

The amount of Lewis acid, Al(Hal)₃ wherein Hal is a halide as definedabove, used in the reaction should be in sufficient amounts to transform2,4,6-trihalo-1,3,5-triazine or 2,4,6-trihalo-pyrimidine to thepreferred 2-halo-4,6-bisbenzocyclic-1,3,5-triazine,2,4,6-trisbenzocyclic-1,3,5-triazine, or2-halo-4,6-bisbenzocyclicpyrimidine, 2,4,6-trisbenzocyclicpyrimidine,respectively. The amount of Lewis acid should be between about 0.5 toabout 500 mol equivalents. Preferably, the amount of Lewis acid shouldbe between about 1 to about 5 mol equivalents.

Advantageously, an acid can be used in conjunction with a Lewis acidwhen synthesizing compounds of Formula (I), (IV a/b/c), (V), (XXXII),(XXXV), or (XXXVI). The amount of acid used in the reaction should be insufficient amounts to transform 2,4,6-trihalo-1,3,5-triazine or2,4,6-trihalopyrimidine to the preferred2-halo-4,6-bisbenzocyclic-1,3,5-triazine or2-halo-4,6-bisbenzocyclicpyrimidine, respectively, or convert2-halo-4,6-bisbenzocyclic-1,3,5-triazine or2-halo-4,6-bisbenzocyclicpyrimidine to the compounds of Formula (I), (IVa/b/c), or (V), as desired. Preferably, the amount of acid should bebetween about 0.01 mol to about 5 mol equivalents.

For all synthetic schemes, the Lewis acid and acid preferably combine toform a mixture that can be prepared in situ or pre-formed prior toaddition to the reagents. The Lewis acid and/or acid can be combinedwith either the benzocyclic compound of Formula (XXX), compounds ofFormula (XXXI) or (XXXIV), or both, in any manner. In situ reactionmixture preparation comprises addition of at least one Lewis acid and atleast one acid to at least one compound of Formula (XXXI) or (XXXIV), atleast one benzocyclic compound of Formula (XXX), and optionally solvent,without regard to addition order. To prepare the mixture prior toaddition to the reagents, i.e., the pre-formed method, at least oneLewis acid and at least one acid are combined and allowed to mix priorto addition, optionally in an inert solvent. Thereafter, the mixture isadded to the reagents or vice versa, as desired and in any additionorder. As used herein, one or more Lewis acids may be used, the firststep and the second step Lewis acid may be the same or different.Additionally, one or more acids may be used, the first step and secondstep acid may be the same or different. In the “continuous” process, theuse of additional Lewis acid, acid, or both is optional.

If the complex is prepared using the pre-formed method, preferred mixingtime of the Lewis acid and acid, prior to addition to the reagents, isbetween about 1 minute to about 5 hours, more preferred time is betweenabout 10 minutes to about 2 hours. The preferred mixing temperature ofthe Lewis acid and acid mixture, prior to addition to the reagents, isbetween about −50° C. to about 100° C., more preferred is between about−10° C. to about −50° C.

The reaction should run for a sufficient amount of time, at a sufficienttemperature and pressure to synthesize the desired triazine orpyrimidine compound. The preferred reaction time for the synthesis ofcompounds of Formula (XXXII), (XXXV), (XXXVI), i.e., the first step, isbetween about 5 minutes and about 48 hours, more preferred between about15 minutes and about 24 hours. The preferred reaction time for thesynthesis of compounds of Formula (I), (IV a/b/c), (V), i.e., the secondstep, is between about 10 minutes and about 24 hours, more preferablytime is between about 30 minutes and about 12 hours. The preferredreaction temperature for the first step is between about −50° C. andabout 150° C., more preferred reaction temperature between about −30° C.and about 50° C. The reaction pressure is not critical and can be about1 atm or higher if desired. Preferably, the reaction is carried outunder an inert gas such as nitrogen or argon. The preferred reactiontemperature for the second step is between about 0° C. and about 120°C., a more preferred reaction temperature is between about 20° C. andabout 100° C.

The step-wise process comprises mixing at least one Lewis acid, at leastone acid, and compounds of Formula (XXXI) or (XXXIV) with one or more ofthe desired benzocyclic compounds of Formula (XXX), preferably until thereaction is between about 70% to about 100% completed. Thereafter, theproduct is isolated and purified. The aromatic compound of Formula(XXXIII) is added to the purified product along with Lewis acid andoptionally an acid to synthesize the compounds of Formula (I), (IVa/b/c), or (V). The step-wise sequence allows for the isolation,purification, and storage of compounds of Formula (XXXII), (XXXV), or(XXXVI) prior to subsequent reaction with aromatic compounds of Formula(XXXIII).

The continuous reaction comprises allowing a compound of Formula (XXXI)or (XXXIV) to react with one or more benzocyclic compounds of Formula(XXX) in the presence of at least one Lewis acid and at least one acidpreferably until the reaction is between about 70% to about 100%complete. Thereafter, without isolating the product of Formula (XXXII),(XXXV), or (XXXVI), the aromatic compound of Formula (XXXIII) is allowedto react with the product of Formula (XXXII), (XXXV), or (XXXVI) in thepresence of optionally at least one second Lewis acid and optionally atleast one second acid preferably until the reaction is between about 70%to about 100% complete. The continuous reaction eliminates the need topurify the intermediate product of Formula (XXXII), (XXXV), or (XXXVI)or use of additional reagents such as solvents, and optionally Lewisacids and acids. Moreover, the one-step process simplifies the syntheticreaction pathway such that no unnecessary handling or processing of thereaction mixture is required until the reaction is completed.

To synthesize compounds of Formula (I), (IV a/b/c) or (V) using thepre-formed method, the preferred addition time of the Lewis acid/acidmixture to a reagent mixture is between about 5 minutes to about 5hours, more preferred time is between about 15 minutes to about 3 hours.The addition temperature of the Lewis acid/acid mixture to a reagentmixture is between about −50° C. to about 150° C., preferred additiontemperature is between about −30° C. to about 50° C., and more preferredaddition temperature is between about −20° C. to about 80° C.

To synthesize compounds of Formula (I), (IV a/b/c), or (V) using thepre-formed method, the preferred addition temperature of the Lewisacid/acid mixture is between about 0° C. to about 100° C., preferredaddition temperature is between about 20° C. to about 80° C.

To synthesize compounds of Formula (I), (IV a/b/c), (V), the preferredaddition time of the aromatic compound of Formula (XXXIII) to thereaction mixture is between about 5 minutes to about 10 hours, morepreferred addition time is between about 10 minutes to about 5 hours,and most preferred addition time is between about 15 minutes to about 2hours. The addition temperature of the aromatic compound of Formula(XXXIII) to the reaction mixture is between about 0° C. to about 150°C., preferred addition temperature is between about 20° C. to about 100°C.

The Lewis acid/acid mixture should be present in amounts sufficient toreact with the number of halogens being substituted on compounds ofFormula (XXXI) or (XXXIV). A range of between about 1 to about 5 molequivalents of Lewis acid and a range of between about 0.01 mol to about5 mol equivalents of acid can be used. The preferred Lewis acid isaluminum chloride. A preferred amount of Lewis acid is between about 2to about 4 mol equivalents to halo-triazine or halo-pyrimidine. Apreferred amount of acid is between about 0.05 mol to about 2 molequivalents to compounds of Formula (XXXI) or (XXXIV).

The synthesis of compounds of Formula (VI), (VII), VIII), or (IX) can beperformed by methods commonly known in the art. One of ordinary skill inthe art with little or no experimentation can determine the appropriateconditions to obtain the polymer product desired.

Uses of the Benzocycle-substituted Pyrimidines and Triazines

As indicated earlier, the novel benzocyclie-substituted pyrimidines andtriazines of the present invention are particularly useful asultraviolet light absorber agents for stabilizing a wide variety ofmaterials including, for example, various polymers (both crosslinked andthermoplastic), photographic materials and dye solutions for textilematerials, as well as in ultraviolet light screening agents (such assunscreens). The novel benzocyclie-substituted pyrimidines and triazinesof the present invention can be incorporated into such material in anyone of a variety of conventional manners, including for example,physical mixing or blending, optionally, with chemical bonding to thematerial (typically to a polymer), as a component in a light stabilizingcomposition such as a coating or solution, or as a component in a UVscreening composition such as a sunscreen composition.

In one embodiment of the present invention, the benzocyclie-substitutedpyrimidines and triazines of the present invention can be employed tostabilize materials which are subject to degradation by ultravioletradiation by incorporating the presently claimed compounds intopolymeric materials, either chemically or physically. Non-limitingexamples of polymeric materials that may be so stabilized arepolyolefins, polyesters, polyethers, polyketones, polyamides, naturaland synthetic rubbers, polyurethanes, polystyrenes, high-impactpolystyrenes, polyacrylates, polymethacrylates, polyacetals,polyacrylonitriles, polybutadienes, polystyrenes, ABS, SAN (styreneacrylonitrile), ASA (acrylate styrene acrylonitrile), cellulosic acetatebutyrate, cellulosic polymers, polyimides, polyamideimides,polyetherimides, polyphenylsulfides, PPO, polysulfones,polyethersulfones, polyvinylchlorides, polycarbonates, polyketones,aliphatic polyketones, thermoplastic TPO's, aminoresin crosslinkedpolyacrylates and polyesters, polyisocyanate crosslinked polyesters andpolyacrylates, phenol/formaldehyde, urea/formaldehyde andmelamine/formaldehyde resins, drying and non-drying alkyd resins, alkydresins, polyester resins, acrylate resins cross-linked with melamineresins, urea resins, isocyanates, isocyanurates, carbamates, and epoxyresins, cross-linked epoxy resins derived from aliphatic,cycloaliphatic, heterocyclic and aromatic glycidyl compounds, which arecross-linked with anhydrides or amines, polysiloxanes, Michael additionpolymers, amines, blocked amines with activated unsaturated andmethylene compounds, ketimines with activated unsaturated and methylenecompounds, polyketimines in combination with unsaturated acrylicpolyacetoacetate resins, polyketimines in combination with unsaturatedacrylic resins, radiation curable compositions, epoxymelamine resins,organic dyes, cosmetic products, cellulose-based paper formulations,photographic film paper, ink, and blends thereof.

The preferred polymeric material is selected from the group consistingof polyolefins; copolymers of one or more monoolefins and/or diolefinswith carbon monoxide and/or with other vinyl monomers; hydrocarbonresins (such as C₅-C₉) including hydrogenated modifications thereof andmixtures of polyalkylenes and starch; polyesters; copolyethers esters;polyethers; polyketones; polyamides and copolyamides derived fromdiamines, dicarboxylic acids and/or aminocarboxylic acids or thecorresponding lactams; natural and synthetic rubbers and elastomers;polyurethanes; polystyrenes, poly-α-methylstyrenes and copolymers withother vinyl monomers; graft copolymers of styrene; high impactpolystyrenes; polyacrylic acids, polymethacrylics acids, polyacrylates,polymethacrylates, polyacrylamides, polyacrylonitriles; homo- andcopolymers derived from unsaturated alcohols and amines or the acylderivatives or acetals thereof such as polyvinyl alcohol, polyvinylacetate, polyacetals, and polybutyrals; homo- and copolymers of cyclicethers such as alkylene glycols and alkylene oxides, as well ascopolymers with bisglycidyl ethers; polybutadienes; polystyrenes; ABS(acrylonitrile butadiene styrene); SAN (styrene acrylonitrile); ASA(acrylate styrene acrylonitrile); cellulosic acetate butyrate;cellulosic polymers; polyureas; polyimides; polyamides-imides;polyester-imides; polyether-imides; polyhydantoins; polybenzimidazoles;polyphenylsulfide; PPO (polypropylene oxide); polysulfones; polyethersulfones; polyether ketones; halogen-containing polymers;polyvinylchlorides; polycarbonates; polyester carbonates; thermoplasticTPO's; amino resin cross-linked polyacrylates and polyesters;polyisocyante cross-linked polyesters and polyacrylates;phenol/formaldehyde, urea/formaldehyde and melamine/formaldehyde resins;saturated and unsaturated polyester resins; cross-linkable acrylicresins derived from substituted acrylates such as epoxy acrylates,hydroxy acrylates, isocyanato acrylates, urethane acrylates or polyesteracrylates; alkyd resins, polyester resins, and acrylate resinscross-linked with melamine resins, urea resins, isocyantes,isocyanurates, carbamates, or epoxy resins; cross-linked epoxy resinsderived from aliphatic cycloaliphatic, heterocyclic and/or aromaticglycidyl compounds which are cross-linked with anhydrides or amines;polysiloxanes; Michael addition polymers of amines or blocked arnines(e.g., ketimines) with activated unsaturated and/or methylene compounds;of ketimines with activated unsaturated and/or methylene compounds suchas acrylates and methacrylates, maleates, and acetoacetates;polyketimines in combination with unsaturated acrylic polyacetoacetateresins or with unsaturated acrylic resins; radiation curablecompositions; epoxymelamine resins; natural polymers such as cellulose,rubber, gelatin, and chemically modified derivatives thereof; organicdyes and pigments; any mixture or blends of the above; cosmeticproducts; cellulose-based paper formulations; photographic film; paper;ink; and intraocular lenses.

Further non-limiting examples of specific polymers which may bestabilized include:

1. Homo- and copolymers of monoolefins and diolefins including but notlimited to ethylene, propylene, isobutylene, butene, methylpentene,hexene, heptene, octene, isoprene, butadiene, hexadiene,dicyclopentadiene, ethylidene and cycloolefins such as cyclopentene andnorbomene; for example, polyethylenes (which optionally can becrosslinked) such as high density polyethylene (HDPE), high density andhigh molecular weight polyethylene (HDPE-HMW), high density andultrahigh molecular weight polyethylene (HDPE-UHMW), medium densitypolyethylene (MDPE), low density polyethylene (LDPE), linear low densitypolyethylene (LLDPE) and branched low density polyethylene (BLDPE).

2. Copolymers of one or more monoolefins and/or diolefins with carbonmonoxide and/or with other vinyl monomers, including acrylic andmethacrylic acid, acrylates and methacrylates, acrylamides,acrylonitriles, styrenes, vinyl acetate (such as ethylene/vinyl acetatecopolymers), vinyl halides, vinylidene halides, maleic anhydride andallyl monomers such as allyl alcohol, allyl amine ally glycidyl etherand derivatives thereof.

3. Hydrocarbon resins (such as C₅-C₉) including hydrogenatedmodifications thereof and mixtures of polyalkylenes and starch.

4. Homo- and copolymers of styrenes such as styrene, p-methylstyrene andα-methylstyrene.

5. Copolymers of one or more styrenes with other vinyl monomers such asolefins and diolefins (e.g., ethylene, isoprene and/or butadiene),acrylic and methacrylic acid, acrylates and methacrylates, acrylamides,acrylonitriles, vinyl acetate (such as ethylene/vinyl acetatecopolymers), vinyl halides, vinylidene halides, maleic anhydride andallyl compounds such as allyl alcohol, allyl amine allyl glycidyl etherand derivatives thereof.

6. Graft copolymers of styrenes on polybutadienes, polybutadiene/styrenecopolymers and polybutadiene/acrylonitrile copolymers; styrene (orα-methylstyrene) and acrylonitrile (or methacrylonitrile) onpolybutadiene; styrene and maleic anhydride on polybutadiene; styrene,acrylonitrile and maleic anhydride or maleimide on polybutadiene;styrene and acrylonitrile on ethylene/propylene/diene copolymers;styrene and acrylonitrile on polyalkyl acrylates or methacrylates; andstyrene and acrylonitrile on acrylate/butadiene copolymers.

7. Halogen-containing polymers such as polychloroprene; chlorinatedrubbers; chlorinated and brominated isobutylene/isoprene copolymers;chlorinated or sulfochlorinated polyethylene; copolymers of ethylene andchlorinated ethylene; epichlorohydrin polymers and copolymers; andpolymers and copolymers of halogen-containing vinyl compounds such asvinyl chloride, vinylidene chloride, vinyl fluoride and/or vinylidenefluoride and other vinyl monomers.

8. Homo- and copolymers derived from α,β-unsaturated acids andderivatives thereof such as acrylic acid, methacrylic acid, acrylates,methacrylates, acrylamides and acrylonitriles.

9. Copolymers of the monomers mentioned in (8) with other unsaturatedmonomers such as olefins and diolefins (e.g., butadiene), styrenes,vinyl halides, maleic anhydride and allyl monomer such as allyl alcohol,allyl amine, allyl glycidyl ether and derivatives thereof.

10. Homo- and copolymers derived from unsaturated alcohols and amines orthe acyl derivatives or acetals thereof, such as vinyl alcohol, vinylacetate, vinyl stearate, vinyl benzoate, vinyl maleate, vinyl butyral,allyl alcohol, allyl amine, allyl glycidyl ether, allyl phthalate andallyl melamine; as well as copolymers of such monomers with otherethylenically unsaturated monomers mentioned above.

For the preceding groups 1-10 of polymers, the present invention furtherencompasses these polymers as prepared by metallocene catalysts.

11. Homo- and copolymers of cyclic ethers such as alkylene glycols andalkylene oxides, as well as copolymers with bisglycidyl ethers.

12. Polyacetals such as polyoxymethylene and those polyoxymethyleneswhich contain ethylene oxide as a comonomer; and polyoxymethylenesmodified with thermoplastic polyurethanes, acrylates and/or MBS.

13. Polyphenylene oxides and sulfides.

14. Polyurethanes derived from hydroxy-functional components such aspolyhydric alcohols, polyethers, polyesters, polyacrylics and/orpolybutadienes on the one hand, and aliphatic and/or aromaticisocyanates on the other, as well as precursors thereof.

15. Polyamides and copolyamides derived from diamines, dicarboxylicacids and/or aminocarboxylic acids or the corresponding lactams, such aspolyamide 4, polyamide 6, polyamide 6/6, polyamide 6/10, polyamide 6/9,polyamide 6/12, polyamide 4/6, polyamide 12/12, polyamide 11 andpolyamide 12; aromatic polyamides starting from m-xylene diamine andadipic acid; polyamides prepared from hexamethylene diamine andisophthalic and/or terephthalic acid and with or without an elastomer asa modifier, for example, poly-2,4,4-trimethylhexamethyleneterephthalamide or poly-m-phenylene isophthalamide; block copolymers ofthe aforementioned polyamides with polyolefins, olefin copolymer,ionomers, chemically bonded or grafted elastomers, or polyethers such aspolyethylene glycol, polypropylene glycol or polytetramethylene glycol;and polyamides condensed during processing (RIM polyamide systems).

16. Polyureas, polyimides, polyamide-imides, polyetherimides,polyesterimides, polyhydantoins and polybenzimidazoles.

17. Polyesters derived from dicarboxylic acids, diols and/orhydroxycarboxylic acids or the corresponding lactones, such aspolyethylene terephthalate, polybutylene terephthalate,poly-1,4-dimethylcyclohexane terephthalate and polyhydroxybenzoates, aswell as block copolyether esters derived from hydroxyl-terminatedethers; PETG; PEN; PTT; and also polyesters modified with polycarbonateor MBS.

18. Polycarbonates and polyester carbonates.

19. Polysulfones, polyether sulfones and polyether ketones.

20. Crosslinked polymers derived from aldehydes condensation resins suchas phenol/formaldehyde resins, urea/formaldehyde resins andmelamine/formaldehyde resins.

21. Drying and non-drying alkyd resins.

22. Unsaturated polyester resins derived from copolyesters of saturatedand unsaturated dicarboxylic acids with polyhydric alcohols and vinylcompounds as crosslinking agents and also halogen-containingmodifications thereof.

23. Crosslinkable acrylic resins derived from substituted acrylates suchas epoxy acrylates, hydroxy acrylates, isocyanato acrylates, urethaneacrylates or polyester acrylates.

24. Alkyd resins, polyester resins and acrylate resins crosslinked withmelamine resins, urea resins, isocyanates, isocyanurates, carbamates orepoxy resins.

25. Crosslinked epoxy resins derived from aliphatic, cycloaliphatic,heterocyclic and/or aromatic glycidyl compounds such as bisphenol A andbisphenol F, which are crosslinked with hardeners such as anhydrides oramines.

26. Natural polymers such as cellulose, rubber, gelatin and chemicallymodified homologous derivatives thereof, including cellulose acetates,cellulose propionates and cellulose butyrates, or the cellulose etherssuch as methyl cellulose, as well as rosins and their derivatives.

27. Polysiloxanes.

28. Michael addition polymers of amines or blocked amines (e.g.,ketimines) with activated unsaturated and/or methylene compounds such asacrylates and methacrylates, maleates and acetoacetates.

29. Mixtures or blends of any of the above, such as PP/EPDM,polyamide/EPDM or ABS, PVC/EVA, PVC/ABS, PVC/MBS, PC/ABS, PBTP/ABS,PC/ASA, PC/PBT, PVC/CPE, PVC/acrylate, POM/thermoplastic PUR,PC/thermoplastic polyurethane, POM/acrylate, POM/MBS, PPO/HIPS,PPO/PA6.6 and copolymers, PATENT/HDPE, PP/HDPE, PP/LDPE, LDPE/HDPE,LDPE/EVA, LDPE/EAA, PATENT/PP, PATENT/PPO, PBT/PC/ABS, PBT/PET/PC andthe like.

30. Polyketimines in combination with unsaturated acrylicpolyacetoacetate resins or with unsaturated acrylic resins includingurethane acrylates, polyether acrylates, vinyl or acryl copolymers withpendant unsaturated groups and acrylated melamines.

31. Radiation curable compositions containing ethylenically unsaturatedmonomers or oligomers and a polyunsaturated aliphatic oligomer.

32. Epoxymelamine resins such as light-stable epoxy resins cross-linkedby an epoxy functional coetherified high solids melamine resin.

Other materials which can be stabilized include, for example:

33. Naturally occurring and synthetic organic materials which may bemixtures of compounds, including mineral oils, animal and vegetablefats, oils and waxes, or oils, fats or waxes based on synthetic esters(e.g., phthalates, adipates, phosphates or trimellitates) and alsomixtures of synthetic esters with mineral oils in any ratio.

34. Aqueous emulsions of natural or synthetic rubber such as naturallatex or lattices of carboxylated styrene/butadiene copolymers.

35. Organic dyes such as azo dyes (diazo, triazo and polyazo),anthraquinones, benzodifuranones, polycyclic aromatic carbonyl dyes,indigoid dyes, polymethines, styryl dyes, di- and triaryl carboniumdyes, phthalocyanines, quinophthalones, sulfur dyes, nitro and nitrosodyes, stilbene dyes, formazan dyes, quinacridones, carbazoles andperylene tetracarboxylic diimides.

36. Cosmetic products, such as skin lotions, collagen creams, sunscreen,facial make-up, etc., comprising synthetic materials such asantioxidants, preservatives, lipids, solvents, surfactants, colorants,antiperspirants, skin conditioners, moisturizers etc.; as well asnatural products such as collagen, proteins, mink oil, olive oil,coconut oil, carnauba wax, beeswax, lanolin, cocoa butter, xanthan gum,aloe, etc.

37. Cellulose-based paper formulations for use, e.g., in newsprint,cardboard, posters, packaging, labels, stationery, book and magazinepaper, bond typing paper, multi-purpose and office paper, computerpaper, xerographic paper, laser and ink-jet printer paper, offset paper,currency paper, etc.

38. Photographic film paper.

39. Ink.

Aliphatic Polyamide

The novel benzocyclie-substituted pyrimidines and triazines of thepresent invention can also be used with aliphatic polyamide polymers. An“Aliphatic polyamide” is a polyamide characterized by the presence ofrecurring carbonamide groups as an integral part of the polymer chainwhich are separated from one another by at least two aliphatic carbonatoms. Illustrative of these polyamides are those having recurringmonomeric units represented by the general formula:

—NHC(O)RC(O)NHR¹— or —NH—R—C(O)—

or a combination hereof in which R and R¹ are the same or different andare alkylene groups of at least about two carbon atoms, preferablyalkylene having from about 2 to about 12 carbon atoms. Exemplary of suchpolyamides are polyamides formed by the reaction of diamines and diacidssuch as poly (tetramethylene adipamide)(nylon 4,6); poly(hexamethyleneadipamide) (nylon 6,6); poly (hexamethylene azelamide) (nylon 6,9);poly(hexamethylene sebacamide) (nylon 6,10); poly(heptamethylenepimelamide) (nylon 8,8); poly(nonamethylene azelamide) (nylon 9,9);poly(decamethylene azelamide) (nylon 10,9); and the like. Alsoillustrative of useful aliphatic polyamides are those formed bypolymerization of amino acids and derivatives thereof, as for examplelactams. Illustrative of these useful polyamides are poly(4-aminobutyricacid) (nylon 4); poly(6-aminohexanoic acid) (nylon 6);poly(7-aminoheptanoic acid) (nylon 7); poly(8-aminoocatanoic acid)(nylon 8); poly(9aminononanoic acid) (nylon 9); poly(10-aminodecanoicacid) (nylon 10); poly(11-aminoundecanoic acid) (nylon 11);poly(12-aminododecanoic acid) (nylon 12); and the like. Blends of two ormore aliphatic polyamides may also be employed.

Copolymers formed from any combination of the recurring units of theabove referenced aliphatic polyamides can be used. By way ofillustration and not limitation, such aliphatic polyamide copolymersinclude caprolactam/hexamethylene adipamide copolymer (nylon 6/6,6);hexamethylene adipamide/caprolactam copolymer (nylon 6, 6/6);hexamethylene adipamide/hexamethylene-azelamide copolymer (nylon6,6/6,9); and copolymers formed from recurring units of the abovereferenced aliphatic polyamides with aliphatic/aromatic polyamiderecurring units may also be used. Examples of such copolyamides arenylon 6/6T; nylon 6,6/6, T; nylon 6/10T; nylon 6/12T; nylon 6,10/6,Tetc.

Preferred aliphatic polyamides for use in the practice of this inventionare poly(caprolactam); poly(7-aminoheptanic acid); poly(tetramethyleneadipamide); poly(hexamethylene adipamide); and mixtures thereof. Theparticularly preferred aliphatic polyamides are poly(caprolatam);poly(hexamethylene adipamide); poly(tetramethylene adipamide); andmixtures thereof.

Aliphatic polyamides useful in the practice of this invention may beobtained from commercial sources or prepared in accordance with knownpreparatory techniques. For example, polycaprolactam may be obtainedfrom Allied Signal Inc. and poly(hexamethylene adipamide) may beobtained from DuPont Co.

The number average molecular weight of the aliphatic polyamide may varywidely. Usually, the aliphatic polyamide is of film forming molecularweight that is sufficiently high to form a free standing film andsufficiently low to allow melt processing of the blend into a film. Suchnumber average molecular weights are well known to those of skill in thefilm art and are usually at least about 5,000 as determined by theformic acid viscosity method. In this method, a solution of 9.2 wt.Concentration of aliphatic polyamide in 90% formic acid at 25° C. isused. In the preferred embodiments of the invention, the number averagemolecular weight of the aliphatic polyamide is from about 5,000 to about1,000,000 and in the particularly preferred embodiments is from about10,000 to about 100,000. Amongst the particularly preferred embodiments,most preferred are those in which the molecular weight of the aliphaticpolyamide is from about 20,000 to about 40,000.

Polyurethane

Polyurethane (PUR) elastomer products (“spandex”) can be stabilizedagainst discoloration and loss of elasticity during UV light exposurewith combinations of UV absorbers according to the invention andhindered amine light stabilizers. Spandex fibers is a PUR elastomerproduct, which requires very specific UV absorber and hindered aminelight stabilizers properties in order to achieve optimum performance. UVabsorbers of the triazine class of this invention can be combined withpolymeric hindered amine light stabilizers (HALS) to provide outstandingperformance in achieving the desired properties for the Spandex fiberapplications.

The triazine UV absorber of the invention, used alone or in combinationwith HALS provides the following properties in the Spandex fiberapplication: (1) low color contribution at typical use levels in the0.5-2.0% range; (2) sufficient MW, thermal stability and low volatilityfor fiber processing and thermal exposure conditions; (3) highcompatibility and permanence; (4) prevent discoloration and loss ofelasticity during exposure to UV light energy; (5) low extraction bywater and dry cleaning solvents; (6) low color development duringexposure to atmospheric pollutants, NO_(x), SO_(x), hydrocarbons, etc.;(7) low interaction with sea water and pool chemicals; (8) lowinteraction and color development with typical phenolic antioxidantsused for the thermal stabilization of Spandex fibers; and (9) lowinteraction with copper based antioxidant systems used in Nylon fibersfor Nylon/Spandex fabrics.

The triazine UV absorber with or without the polymeric HALS providesoutstanding stabilization with minimum negative effect on secondaryperformance properties, such as low color development during NO_(x)exposure and low interaction with copper based antioxidant systems usingin Nylon fibers.

As noted above, any of the triazine compounds disclosed herein can beused to impart one or more of the properties described above to Spandexfibers when added thereto in a stabilization effective amount.

Preferably, these triazine compounds are added in combination withpolymeric HALS. The polymeric HALS is preferablypoly[(6-morpholino-s-triazine-2,4-diyl)[2,2,6,6,-tetramethyl-4-piperidyl)imino]-hexamethylene[(2,2,6,6-tetramethyl-4-piperidyl)imino]]. Most preferably, thepolymeric HALS is the methylated (M) version of the above HALS, which issold by Cytec Industries, Inc. as CYASORB®UV-3529 light stabilizer.Other polymeric HALS disclosed in U.S. Pat. No. 4,331,586 are alsosuitable.

Spandex fibers are made from a polyurethane (PUR) prepolymer preparedfrom a diisocyanate and a glycol. There are four basic processes used toconvert the PUR prepolymer into the fiber product. These processes areSolution Dry Spinning, Solution Wet Spinning, Melt Extrusion, andReaction Spinning. The above UV stabilizer alone or in combination withHALS would be suitable for use in any or all four processes.

Spandex fibers may contain a processing antioxidant system, such as aphenolic antioxidant, or a phenolic/phosphite antioxidant combination.In addition, pigments, such as TiO₂ are commonly used in the fiberproducts.

The triazine UV absorber alone or with M-HALS can be dissolved into DMFor DMAC and added to the PUR prepolymer solution prior to solution fiberspinning processes. Also, the combination can be extrusion compoundedinto the PUR compound used in the melt spinning process.

Polycarbonates

Among polymeric materials to be stabilized with the novelbenzocycle-substituted pyrimidines and triazines of the presentinvention, preference is given to the polycarbonates, polyesters,polyamides, polyacetals, polyphenylene oxides and polyphenylenesulfides, but especially to the polycarbonates. Those compounds are tobe understood as being especially those polymers the constitutionalrepeating unit of which corresponds to the formula:

wherein A is a divalent phenolic radical. Examples of A are given interalia in U.S. Pat. No. 4,960,863 and

DE-A-3 922,496. A can be derived, for example, from hydroquinone,resorcinol, dihydroxybiphenylene or bisphenols in the broadest sense ofthe term, such as bis(hydroxyphenyl)alkanes, cycloalkanes, sulfides,ethers, ketones, sulfones, sulfoxides,α,α′-bis(hydroxyphenyl)-diisopropylbenzenes, for example the compounds2,2-bis(4-hydroxyphenyl)propane,2,2-bis(3,5-dimethyl-4-hydroxyphenyl)-propane,2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, or from the compounds of the formulae:

In one embodiment, the preferred resins are polycarbonates based ondihydric phenols such as 2,2-bis-(4-hydroxyphenyl)propane (bisphenol A);2,4-bis (4-hydroxyphenyl)-2-methylbutane;1,1-bis-(4-hydroxyphenyl)-cyclohexane;2,2-bis-(3-chloro-4-hydroxyphenyl)propane; 4,4′-sulfonyldiphenol; and1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

Also preferred are polycarbonate copolymers incorporating two or morephenols, branched polycarbonates wherein a polyfunctional aromaticcompounds is reacted with the dihydric phenol(s) and carbonateprecursor, and polymer blends of which polycarbonate comprises asignificant portion of the blend.

The most preferred resins for both layers are polycarbonates based onbisphenol A.

U.S. Pat. No. 5,288,788 also describes polycarbonates and polyestercarbonates, especially aromatic polycarbonates, for example those basedon 2,2-bis(4-hydroxyphenyl)propane or1,1-bis(4-hydroxyphenyl)cyclohexane.

Multilayer Systems

British Patent Application No. 2,290,745 describes a number of methodshave been developed to concentrate UV absorbers near or at the surfaceof polymeric materials. These include surface impregnation (see U.S.Pat. Nos. 3,309,220, 3,043,709, 4,481,664 and 4,937,026) and coating aplastic article with solutions containing thermoplastic resins and UVabsorbers (see U.S. Pat. Nos. 4,668,588 and 4,353,965). Both techniquessuffer from drawbacks including requiring additional processing steps(i.e. applying, drying or curing), and encounter difficulties associatedwith the handling of large processed articles. An additional drawback,particularly relevant to polycarbonate sheet production, is thedetrimental effect such post addition treatment would have on thesurface of the polymeric substrate.

As described in the U.S. Pat. No. 5,445,872, application of surfacelayers via coextrusion takes place in a known manner in knowncoextrusion equipment as taught in U.S. Pat. Nos. 3,487,505 and3,557,265. Coextrusion is a well recognized method of producinglaminated thermoplastic materials by simultaneously extruding variousnumbers of layers which form a single composite material. U.S. Pat. No.4,540,623 describes coextruded materials of at least forty layers. Othermethods produce as few as two or three different layers.

In one embodiment, the invention also relates to thermoplastic articlescoated with a thermoplastic layer 0.1 to 10 mil (0.00254 mm to 0.254mm), preferable 0.1 to 5 mil (0.00254 mm to 0.127 mm), thick, in whichsaid layer contains 0.1% to 20% by weight of the benzocyclie-substitutedpyrimidines and triazines of the present invention. Preferredconcentrations of are 2% to 15% by weight; most preferred concentrationsof 5% to 10% by weight.

The benzocycle-substituted pyrimidines and triazines of the presentinvention may be incorporated into the thermoplastics of the surfaceslayer by standard methods such as dry mixing the additives with granularresin prior to extruding.

The benzocycle-substituted pyrimidine or triazine layer may be appliedto one or both sides of the thermoplastic article.

Laminated thermoplastic articles which contain additional layers such asa water resistant layer as found in U.S. Pat. No. 4,992,322 are alsopart of the present invention.

The core layer and the coating layer may be the same or differentthermoplastic resin including polyesters, polyester carbonates,polyphenylene oxide, polyvinyl chloride, polypropylene, polypropylene,polyethylene, polyacrylates, polymethacrylates and copolymers and blendssuch as styrene and acrylonitrile on polybutadiene and styrene withmaleic anhydride, and mixtures (polyblends) of such polymers with oneanother or with other polymers, for example with polyolefins,polyacrylates, polydienes or other elastomers in the form of impactstrength modifiers.

Bondable Stabilizers

The benzocycle-substituted pyrimidines and triazines of the presentinvention can also be chemically bonded to substrates, such as polymers,thereby greatly reducing the migration of such UV absorbers, e.g., outof the substrate or away from the substrate surface. The bondingmechanism of the triazines of the present invention involves theformation of a bond (chemical and/or co-valent) between a functionalityattached to the amido or carbamate group, e.g., by a pendant vinyl orhydroxyl group, and the “host” substrate, such as a polymer.

Incorporation of the benzocycle-substituted pyrimidines and triazines ofthe invention can be brought about by copolymerization, copolyaddition,copolycondensation, by reaction with a polymer which carries suitablefunctional groups, or by grafting, in a manner as disclosed in U.S. Pat.Nos. 3,423,360 and 5,189,084 which are incorporated herein by referenceas if fully set forth.

Bonding of the benzocycle-substituted pyrimidines and triazines of theinvention can occur by polymerization or copolymerization. In the caseof the novel triazines of the present invention comprising pendant vinylgroups, polymerization or copolymerization with at least one vinylmonomer, e.g., (meth)acrylic acid, esters of (meth)acrylic acid such asmethyl acrylate, amides of (meth)acrylic acid, hydroxyethylacrylate,olefins, vinyl chloride, styrene, butadiene, isoprene and acrylonitrilecan be carried out to form homopolymers or copolymers in which the vinylgroup is incorporated into the backbone of the polymer. Polymerizationor copolymerization can be initiated by initiators, such as freeradical, anionic and cationic types, or by actinic radiation, such asUV, electron beam, x-rays and gamma irradiation from a Co⁶⁰ source, asis well known to those in the polymerization art. Polymerization orcopolymerization can be carried out in solution, in an emulsion, in adispersion, in the melt, or in the solid state as is well known to thosein the polymerization art.

Also, bonding of the presently claimed benzocycle-substitutedpyrimidines and triazines compounds of the present invention can bebrought about by copolyaddition or copolycondensation. Suchincorporation can be made by addition during the synthesis of anaddition polymer or copolymer or by condensation during the synthesis ofa condensation polymer or copolymer by methods known to those skilled inthe art. For example, compounds of the formula (I), (II), or (IV)-(IX)containing the appropriate functional groups can be incorporated intopolyesters, polyamides, polyurethanes, epoxy resins, melamine resins,alkyd resins, phenolic resins, polyurethanes, polycarbonates,polysiloxanes, polyacetals and polyanhydrides, to name but a few.

In addition, compounds of the formula (I), (II), or (IV)-(IX) can bebonded to a monomeric component which is then incorporated into apolymer or copolymer, e.g., by the free radical initiated addition orcopolycondensation methods described above. Analogous methods aredisclosed in, for example, U.S. Pat. No. 5,459,222 (incorporated byreference herein for all purposes as if fully set forth) for the bondingof benzotriazole and benzophenone stabilizers to diol precursors whichare then incorporated by condensation polymerization into polyurethanesand polyesters to impart UV stabilizing properties to said polymers.

Alternately, the benzocycle-substituted pyrimidines and triazines of theinvention may also be bonded to polymers by reaction with an oligomerand/or polymer which carries suitable functional groups. For example, atleast one triazine compound comprising a vinyl pendant group can beadded, optionally with at least one other vinyl monomer or compoundcomprising a vinyl group, to unsaturated polyester resins, unsaturatedpolybutadiene oligomers or unsaturated rubbers and then cured by actinicradiation or by a free radical catalyst. Or, at least one triazinecompound comprising a terminal functional group, such as hydroxyl oramido, may be reacted with a polymer and/or oligomer such as polyesters,polyurethanes and polydiols with reactive end-groups, partiallyhydrolyzed polyvinylacetate, epoxy resins, polysiloxanes and polymerscomprising maleic anhydride, either in the main chain or as aside-chain, by methods analogous to those well known to those ofordinary skill in the art.

Grafting is yet another way of bonding of the presently claimedbenzocycle-substituted pyrimidines and triazines to polymers and/oroligomers. Grafting may be carried out in solution, in the melt, or inthe solid state with the initiators or actinic radiation types discussedabove for polymerization when, for example, the novel triazines of thepresent invention comprising pendant vinyl groups are used. Suchbenzocycle-substituted pyrimidines and triazines may be grafted tosaturated polymers, e.g., polyolefins and their copolymers such aspolyethylene, polypropylene and poly(ethylene-vinyl acetate), or topolymers comprising unsaturated moieties, e.g., polybutadiene,polyisoprene, ethylene-propylene-(diene monomer) terpolymers andpolystyrene and its copolymers.

The benzocycle-substituted pyrimidines and triazines of the presentinvention may be used in widely varying amounts in such applicationsdepending upon such things as the material to be stabilized and theparticular application. However, when employed as a stabilizing additivefor materials such as organic polymers, the benzocycle-substitutedpyrimidines and triazines of the present invention are typicallyemployed in amounts from about 0.01 to about 20% by weight, preferablyfrom about 0.1 to about 10% by weight, and most preferably from about0.1 to about 5% by weight, based on the weight of the material to bestabilized. In screening applications such as sunscreening compositions,the triazines are utilized in the same relative amounts but based on thetotal weight of the screening agent.

The novel stabilizers of the present invention may also be employed in anon-bondable capacity, for example, in the stabilization ofthermoplastic polymers as set forth in the many of the previouslyincorporated references. Examples of preferred thermoplastic polymersare polyolefins and polymers comprising heteroatoms in the main chain.Preferred polymers are also thermoplastic polymers comprising nitrogen,oxygen and/or sulphur, especially nitrogen or oxygen, in the main chain.Also of interest are compositions in which the polymer is a polyolefin,for example polyethylene or polypropylene.

Incorporation into the thermoplastic polymers can be carried out byaddition of the novel benzocycle-substituted triazine or pyrimidinecompound and any further additives by the methods conventional in theart. The incorporation can expediently be made before or during shaping,for example by mixing the pulverulent components or by adding thestabilizer to the melt or solution of the polymer, or by applying thedissolved or dispersed compounds to the polymer, with or withoutsubsequent evaporation of the solvent. Elastomers can also be stabilizedas lattices.

The novel mixtures can also be added to the polymers to be stabilized inthe form of a masterbatch which comprises these compounds, for example,in a concentration of from about 2.5 to about 25%, preferably from about5 to about 20% by weight of the polymer.

The novel mixtures can expediently be incorporated into the polymericmaterial by any number of methods, including those conventionallyemployed in the art, including by, for example: a) as an emulsion ordispersion (for example to lattices or emulsion polymers); (b) as a drymix during mixing of additional components or polymer mixtures; (c) bydirect addition to the processing equipment (for example extruders,internal mixers, etc.); or (d) as a solution or melt.

The stabilized polymer compositions obtained in this way can beconverted into shaped articles, for example fibers, films, tapes,sheets, sandwich boards, containers, pipes and other profiles, by anynumber of conventional methods, for example hot pressing, spinning,extrusion, roto-molding or injection molding. Therefore, the presentinvention additionally relates to the use of the polymer compositionaccording to the invention for the production of a shaped article.

Depending upon their ultimate end use, the benzocycle-substitutedpyrimidines and triazines of the present invention may be combined witha variety of additives conventionally employed in the UV stabilizingart. Examples of such additives include but are not limited to:

a. Antioxidants

(i) Alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol;2-tert-butyl-4,6-dimethylphenol; 2,6-di-tert-butyl-4-ethylphenol;2,6-di-tert-butyl-4-n-butylphenol; 2,6-di-tert-butyl-4-isobutylphenol;2,6-dicyclopentyl-4-methylphenol;2-(α-methylcyclohexyl)-4,6-dimethylphenol;2,6-dioctadecyl-4-methylphenol; 2,4,6-tricyclohexylphenol;2,6-di-tert-butyl-4-methoxymethylphenol; nonylphenols which are liner orbranched in the side chains such as 2,6-di-nonyl-4-methylphenol;2,4-dimethyl-6-(1-methylundec-1-yl)phenol;2,4-dimethyl-6-(1-methylheptadec-1-yl)phenol;2,4-dimethyl-6-(1-methyltridec-1-yl)phenol; and mixtures thereof.

(ii) Alkylthiomethylphenols such as2,4-dioctylthiomethyl-6-tert-butylphenol;2,4-dioctylthiomethyl-6-methylphenol;2,4-dioctylthiomethyl-6-ethylphenol; and2,6-di-dodecylthiomethyl-4-nonylphenol.

(iii) Hydroquinones and alkylated hydroquinones such as2,6-di-tert-butyl-4-methoxyphenol; 2,5-di-tert-butylhydroquinone;2,5-di-tert-amylhydroquinone; 2,6-diphenyl-4-octadecyloxyphenol;2,6-di-tert-butylhydroquinone; 2,5-di-tert-butyl-4-hydroxyanisole;3,5-di-tert-butyl-4-hydroxyanisole; 3,5-di-tert-butyl-4-hydroxyphenylstearate; and bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate.

(iv) Tocopherols such as α-tocopherol, β-tocopherol, γ-tocopherol,δ-tocopherol, and mixtures thereof (vitamin E).

(v) Hydroxylated thiodiphenyl ethers such as2,2′-thiobis(6-tert-butyl-4-methylphenol); 2,2′-thiobis(4-octylphenol);4,4′-thiobis(6-tert-butyl-3-methylphenol);4,4′-thiobis(6-tert-butyl-2-methylphenol);4,4′-thiobis(3,6-di-sec-amylphenol); and4,4′-bis(2,6-dimethyl-4-hydroxyphenyl)disulfide.

(vi) Alkylidenebisphenols such as2,2′-methylenebis(6-tert-butyl-4-methylphenol);2,2′-methylenebis(6-tert-butyl-4-ethylphenol);2,2′-methylenebis[4-methyl-6-(α-methylcyclohexyl)phenol];2,2′-methylenebis(4-methyl-6-cyclohexylphenol);2,2′-methylenebis(6-nonyl-4-methylphenol);2,2′-methylenebis(4,6-di-tert-butylphenol);2,2′-ethylidenebis(4,6-di-tert-butylphenol);2,2′-ethylidenebis(6-tert-butyl-4-isobutylphenol);2,2′-methylenebis[6-(α-methylbenzyl)-4-nonylphenol];2,2′-methylenebis[6-(α,α-dimethylbenzyl)-4-nonylphenol];4,4′-methylenebis(2,6-di-tert-butylphenol);4,4′-methylenebis(6-tert-butyl-2-methylphenol);1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)butane;2,6-bis(3-tert-butyl-5-methyl-2-hydroxylbenzyl)-4-methylphenol;1,1,3-tris(5-tert-butyl-4-hydroxy-2-methylphenyl)butane;1,1-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercaptobutane;ethylene glycol bis[3,3-bis(3′-tert-butyl-4′-hydroxyphenyl)butyrate],bis(3-tert-butyl-4-hydroxy-5-methylphenyl)dicyclopentadiene;bis[2-(3′-tert-butyl-2′-hydroxy-5′-methylbenzyl)-6-tert-butyl-4-methylphenyl]terephthalate;1,1-bis(3,5-dimethyl-2-hydroxyphenyl)butane;2,2-bis(3,5-di-tert-butyl-4-hydroxyphenyl)propane;2,2-bis(5-tert-butyl-4-hydroxy-2-methylphenyl)-4-n-dodecylmercaptobutane;and 1,1,5,5-tetra(5-tert-butyl-4-hydroxy-2-methylphenyl)pentane.

(vii) O—, N— and S-benzyl compounds such as3,5,3′,5′-tetra-tert-butyl-4,4′-dihydroxydibenzyl ether;octadecyl-4-hydroxy-3,5-dimethylbenzylmercaptoacetate;tridecyl-4-hydroxy-3,5-di-tert-butylbenzylmercaptoacetate;tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine;bis(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)dithioterephthalate;bis(3,5-di-tert-butyl-4-hydroxybenzyl)sulfide; andisooctyl-3,5-di-tert-butyl-4-hydroxybenzylmercaptoacetate.

(viii) Hydroxybenzylate malonates such asdioctadecyl-2,2-bis(3,5-di-tert-butyl-2-hydroxybenzyl)malonate;dioctadecyl-2-(3-tert-butyl-4-hydroxy-5-methylbenzyl)malonate;didodecylmercaptoethyl-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate;andbis[4-(1,1,3,3-tetramethylbutyl)phenyl]-2,2-bis(3,5-di-tert-butyl-4-hydroxybenzyl)malonate.

(ix) Aromatic hydroxybenzyl compounds such as1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene;1,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)-2,3,5,6-tetramethylbenzene;and 2,4,6-tris(3,5-di-tert-butyl-4-hydroxybenzyl)phenol.

(x) Triazine compounds such as2,4-bis(octylmercapto-6-(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine;2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyanilino)-1,3,5-triazine;2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine;2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenoxy)-1,3,5-triazine;1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate;1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate;2,4,6-tris(3,5-di-tert-butyl-4-hydroxyphenylethyl)-1,3,5-triazine;1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)-hexahydro-1,3,5-triazine;and 1,3,5-tris(3,5-dicyclohexyl-4-hydroxybenzyl)isocyanurate.

(xi) Benzylphosphonates such asdimethyl-2,5-di-tert-butyl-4-hydroxybenzylphosphonate;diethyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate;dioctadecyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate;dioctadecyl-5-tert-butyl-4-hydroxy-3-methylbenzylphosphonate; and thecalcium salt of the monoethyl ester of3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid.

(xii) Acylaminophenols such as 4-hydroxylauranilide;4-hydroxystearanilide; and octylN-(3,5-di-tert-butyl-4-hydroxyphenyl)carbamate.

(xiii) Esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acidwith mono- or polyhydric alcohols such as methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

(xiv) Esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acidwith mono- or polyhydric alcohols such as methanol, ethanol, n-octanol,i-octanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

(xv) Esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid withmono- or polyhydric alcohols such as methanol, ethanol, octanol,octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol,1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethyleneglycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl)isocyanurate, N,N′-bis(hydroxyethyl)-oxamide, 3-thiaundecanol,3-thiapentadecanol, trimethylhexanediol, trimethylolpropane and4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

(xvi) Esters of 3,5-di-tert-butyl-4-hydroxyphenyl acetic acid with mono-or polyhydric alcohols such as methanol, ethanol, octanol, octadecanol,1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol,neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethyleneglycol, pentaerythritol, tris(hydroxyethyl) isocyanurate,N,N′-bis-(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol,trimethylhexanediol, trimethylolpropane,4-hydroxymethyl-1-phospha-2,6,7-trioxabicyclo[2.2.2]octane.

(xvii) Amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acidsuch asN,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hexamethylenediamine;N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)trimethylenediamine;and N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine.

(xviii) Ascorbic acid (Vitamin C).

(xix) Aminic antioxidants such as N,N′-diisopropyl-p-phenylenediamine;N,N′-di-sec-butyl-p-phenylenediamine;N,N′-bis(1,4-dimethylpentyl)-p-phenylenediamine;N,N′-bis(1-ethyl-3-methylpentyl)-p-phenylenediamine;N,N′-bis(1-methylheptyl)-p-phenylenediamine;N,N′-dicyclohexyl-p-phenylenediamine; N,N′-diphenyl-p-phenylenediamine;N,N′-bis(2-naphthyl)-p-phenylenediamine;N-isopropyl-N′-phenyl-p-phenylenediamine;N-(1,3-dimethylbutyl)-N′-phenyl-p-phenylenediamine;N-(1-methylheptyl)-N′-phenyl-p-phenylenediamine;N-cyclohexyl-N′-phenyl-p-phenylenediamine;4-(p-toluenesulfonamoyl)diphenylamine;N,N′-dimethyl-N,N′-di-sec-butyl-p-phenylenediamine; diphenylamine;allyldiphenylamine; 4-isopropoxydiphenylamine; -phenyl-1-naphthylamine;N-(4-tert-octylphenyl)-1-naphthylamine; N-phenyl-2-naphthylamine;octylated diphenylamine such as p,p′-di-tert-octyldiphenylamine;4-n-butylaminophenol; 4-butyrylaminophenol; 4-nonanoylaminophenol;4-dodecanoylaminophenol; 4-octadecanoylaminophenol;bis(4-methoxyphenyl)amine;2,6-di-tert-butyl-4-dimethylaminomethylphenol;2,4′-diaminophenylmethane; 4,4′-diaminodiphenylmethane;N,N,N′,N′-tetramethyl-4,4′-diaminodiphenylmethane;1,2-bis[(2-methylphenyl)amino]ethane; 1,2-bis(phenylamino)propane;(o-tolyl)biguanide; bis[4-(1′,3′-dimethylbutyl)phenyl]amine;tert-octylated N-phenyl-1-naphthylamine; a mixture of mono- anddialkylated tert-butyl/tert-octyldiphenylamines, a mixture of mono- anddialkylated nonyldiphenylamines; a mixture of mono- and dialkylateddodecyldiphenylamines; a mixture of mono- and dialkylatedisopropyl/isohexyldiphenylamines, a mixture of mono- and dialkylatedtert-butyldiphenylamines; 2,3-dihydro-3,3-dimethyl-4H-1,4-benzothiazine;phenothiazine; a mixture of mono- and dialkylated tert-butyl/tert-octylphenothiazines; a mixture of mono- and dialkylatedtert-octylphenothiazines; N-allylphenothiazine;N,N,N′,N′-tetraphenyl-1,4-diaminobut-2-ene;N,N-bis(2,2,6,6-tetramethylpiperid-4-yl)hexamethylenediamine;bis(2,2,6,6-tetramethylpiperid-4-yl)sebacate;2,2,6,6-tetramethylpiperidin-4-one; and2,2,6,6-tetramethylpiperidin-4-ol.

b. UV-absorbers and Light Stabilizers

(i) 2-(2′-Hydroxyphenyl)benzotriazoles such as2-(2′-hydroxy-5′-methylphenyl)-benzotriazole;2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)benzotriazole;2-(5′-tert-butyl-2′-hydroxyphenyl)benzotriazole;2-(2′-hydroxy-5′-(1,1,3,3-tetramethylbutyl)phenyl)benzotriazole;2-(3′,5′-di-tert-butyl-2′-hydroxyphenyl)-5-chlorobenzotriazole;2-(3′-tert-butyl-2′-hydroxy-5′-methylphenyl)-5-chloro-benzotriazole;2-(3′-sec-butyl-5′-tert-butyl-2′-hydroxyphenyl)-benzotriazole;2-(2′-hydroxy-4′-octoxyphenyl)benzotriazole;2-(3′,5′-di-tert-amyl-2′-hydroxphenyl)benzotriazole;2-(3′,5′-bis(α,α-dimethylbenzyl)-2′-hydroxyphenyl)-benzotriazole; amixture of2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)-carbonylethyl]-2′-hydroxyphenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)-5-chloro-benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-methoxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-2′-hydroxy-5′-(2-octyloxycarbonylethyl)phenyl)benzotriazole,2-(3′-tert-butyl-5′-[2-(2-ethylhexyloxy)carbonylethyl]-2′-hydroxyphenyl)benzotriazole,2-(3′-dodecyl-2′-hydroxy-5′-methylphenyl)benzotriazole and2-(3′-tert-butyl-2′-hydroxy-5′-(2-isooctyloxycarbonylethyl)phenylbenzotriazole;2,2-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-benzotriazol-2-ylphenol];the transesterification product of2-[3′-tert-butyl-5′-(2-methoxycarbonylethyl)-2′-hydroxyphenyl]benzotriazolewith polyethylene glycol 300; and [R—CH₂CH—COO(CH₂)₃]₂B whereR=3′-tert-butyl-4′-hydroxy-5′-2H-benzotriazol-2-ylphenyl.

(ii) 2-Hydroxybenzophenones, for example the 4-hydroxy, 4-methoxy,4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2′,4′-trihydroxy and2′-hydroxy-4,4′-dimethoxy derivative.

(iii) Esters of substituted and unsubstituted benzoic acids such as4-tert-butyl-phenyl salicylate; phenyl salicylate; octylphenylsalicylate; dibenzoyl resorcinol; bis(4-tert-butylbenzoyl) resorcinol;benzoyl resorcinol; 2,4-di-tert-butylphenyl3,5-di-tert-butyl-4-hydroxybenzoate; hexadecyl3,5-di-tert-butyl-4-hydroxybenzoate; octadecyl3,5-di-tert-butyl-4-hydroxybenzoate; and2-methyl-4,6-di-tert-butylphenyl 3,5-di-tert-butyl-4-hydroxybenzoate.

(iv) Acrylates such as ethyl α-cyano-β,β-diphenylacrylate; isooctylα-cyano-β,β-diphenylacrylate; methyl α-carbomethoxycinnamate; methylα-cyano-β-methyl-p-methoxycinnamate; butylα-cyano-β-methyl-p-methoxycinnamate; methylα-carbomethoxy-p-methoxycinnamate; andN-(β-carbomethoxy-β-cyanovinyl)-2-methylindoline.

(v) Nickel compounds such as nickel complexes of2,2′-thio-bis-[4-(1,1,3,3-tetramethylbutyl)phenol], including the 1:1 or1:2 complex, with or without additional ligands such as n-butylamine,triethanolamine or N-cyclohexyldiethanolamine; nickeldibutyldithiocarbamate; nickel salts of monoalkyl esters including themethyl or ethyl ester of 4-hydroxy-3,5-di-tert-butylbenzylphosphonicacid; nickel complexes of ketoximes including 2-hydroxy-4-methylphenylundecyl ketoxime; and nickel complexes of1-phenyl-4-lauroyl-5-hydroxypyrazole, with or without additionalligands.

(vi) Sterically hindered amines as well as the N derivatives thereof(e.g., N-alkyl, N-hydroxy, N-alkoxy and N-acyl), such asbis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate;bis(2,2,6,6-tetramethylpiperidin-4-yl)succinate;bis(1,2,2,6,6-pentamethylpiperidin-4-yl)sebacate;bis(1-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl)sebacate;bis(1,2,2,6,6-pentamethylpiperidin-4-yl) n-butyl3,5-di-tert-butyl-4-hydroxybenzylmalonate; the condensate of1-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinicacid; the condensate ofN,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and4-tert-octylamino-2,6-dichloro-1,3,5-triazine;tris(2,2,6,6-tetramethylpiperidin-4-yl) nitrilotriacetate;tetrakis(2,2,6,6-tetramethylpiperidin-4-yl)-1,2,3,4-butanetetracarboxylate;1,1′-(1,2-ethanediyl)bis(3,3,5,5-tetramethylpiperazinone);4-benzoyl-2,2,6,6-tetramethylpiperidine;4-stearyloxy-2,2,6,6-tetramethylpiperidine;bis(1,2,2,6,6-pentamethylpiperidyl)-2-n-butyl-2-(2-hydroxy-3,5-di-tert-butylbenzyl)malonate;3-n-octyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decan-2,4-dione;bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)sebacate;bis(1-octyloxy-2,2,6,6-tetramethylpiperidyl)succinate; the condensate ofN,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and4-morpholino-2,6-dichloro-1,3,5-triazine; the condensate of2-chloro-4,6-bis(4-n-butylamino-2,2,6,6-tetramethylpiperidyl)-1,3,5-triazineand 1,2-bis(3-aminopropylamino)ethane; the condensate of2-chloro-4,6-bis(4-n-butylamino-1,2,2,6,6-pentamethylpiperidyl)-1,3,5-triazineand 1,2-bis-(3-aminopropylamino)ethane;8-acetyl-3-dodecyl-7,7,9,9-tetramethyl-1,3,8-triazaspiro[4.5]decane-2,4-dione;3-dodecyl-1-(2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione;3-dodecyl-1-(1-ethanoyl-2,2,6,6-tetramethylpiperidin-4-yl)pyrrolidin-2,5-dione;3-dodecyl-1-(1,2,2,6,6-pentamethylpiperidin-4-yl)pyrrolidine-2,5-dione;a mixture of 4-hexadecyloxy- and4-stearyloxy-2,2,6,6-tetramethylpiperidine; the condensate ofN,N′-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexamethylenediamine and4-cyclohexylamino-2,6-dichloro-1,3,5-triazine; the condensate of1,2-bis(3-aminopropylamino)ethane, 2,4,6-trichloro-1,3,5-triazine and4-butylamino-2,2,6,6-tetramethylpiperidine (CAS Reg. No. [136504-96-6]);2-undecyl-7,7,9,9-tetramethyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decane;oxo-piperanzinyl-triazines or so-called PIP-T HALS, e.g., GOODRITE®3034, 3150 and 3159 and similar materials disclosed in U.S. Pat. No.5,071,981; photobondable HALS such as SANDUVOR® PR-31 and PR-32(Clariant Corp.) and similar materials disclosed in GB-A-2269819; andthe reaction product of7,7,9,9-tetramethyl-2-cycloundecyl-1-oxa-3,8-diaza-4-oxospiro[4.5]decaneand epichlorohydrin. See also generally U.S. Pat. Nos. 4,619,956,5,106,891, GB-A-2269819, EP-A-0309400, EP-A-0309401, EP-A-0309402 andEP-A-0434608.

(vii) Oxamides such as 4,4′-dioctyloxyoxanilide; 2,2′-diethoxyoxanilide;2,2′-dioctyloxy-5,5′-di-tert-butoxanilide;2,2′-didodecyloxy-5,5′-di-tert-butyloxanilide;2-ethoxy-2′-ethyloxanilide; N,N′-bis(3-dimethylaminopropyl)oxamide;2-ethoxy-5-tert-butyl-2′-ethyloxanilide and its mixture with2-ethoxy-2′-ethyl-5,4′-di-tert-butoxanilide; and mixtures of o- andp-methoxy disubstituted oxanilides and mixtures of o- and p-ethoxydisubstituted oxanilides.

(viii) 2-(2-Hydroxyphenyl)-1,3,5-triazines disclosed in the previouslyincorporated references, such as2,4,6-tris(2-hydroxy-4-octyloxyphenyl)-1,3,5-triazine;2-(2-hydroxy-4-n-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2-(2-hydroxy-4-(mixediso-octyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2,4-bis(2-hydroxy-4-propyloxyphenyl)-6-(2,4-dimethylphenyl)-1,3,5-triazine;2-(2-hydroxy-4-octyloxyphenyl)-4,6-bis(4-methylphenyl)-1,3,5-triazine;2-(2-hydroxy-4-dodecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2-(2-hydroxy-4-tridecyloxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2-[2-hydroxy-4-(2-hydroxy-3-butyloxypropyloxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2-[2-hydroxy-4-(2-hydroxy-3-octyloxypropyloxy)-phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2-[4-dodecyloxy/tridecyloxy-2-hydroxypropoxy)-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2-[2-hydroxy-4-(2-hydroxy-3-dodecyloxypropoxy)phenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine;2-(2-hydroxy-4-hexyloxy)phenyl-4,6-diphenyl-1,3,5-triazine;2-(2-hydroxy-4-methoxyphenyl)-4,6-diphenyl-1,3,5-triazine;2,4,6-tris[2-hydroxy-4-(3-butoxy-2-hydroxypropoxy)phenyl]-1,3,5-triazine;and 2-(2-hydroxyphenyl)-4-(4-methoxyphenyl)-6-phenyl-1,3,5-triazine.

(c) Metal deactivators such as N,N′-diphenyloxamide;N-salicylal-N′-salicyloyl hydrazine; N,N′-bis(salicyloyl)hydrazine;N,N′-bis(3,5-di-tert-butyl-4-hydroxyphenylpropionyl)hydrazine;3-salicyloylamino-1,2,4-triazole; bis(benzylidene)oxalyl dihydrazide;oxanilide; isophthaloyl dihydrazide; sebacoyl bisphenylhydrazide;N,N′-diacetyladipoyl dihydrazide; N,N′-bis(salicyloyl)oxalyldihydrazide; and N,N′-bis(salicyloyl)thiopropionyl dihydrazide.

(d) Phosphites and phosphonites, such as triphenyl phosphite; diphenylalkyl phosphites; phenyl dialkyl phosphites; tris(nonylphenyl)phosphite; trilauryl phosphite; trioctadecyl phosphite; distearylpentaerythritol diphosphite; tris(2,4-di-tert-butylphenyl)phosphite;diisodecyl pentaerythritol diphosphite;bis(2,4,-di-tert-butylphenyl)pentaerythritol diphosphite;bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite;bis(isodecyloxy)pentaerythritol diphosphite;bis(2,4-di-tert-butyl-6-methylphenyl)pentaerythritol diphosphite;bis(2,4,6-tris(tert-butyl)phenyl)pentaerythritol diphosphite; tristearylsorbitol triphosphite;tetrakis(2,4-di-tert-butylphenyl)-4,4′-biphenylene diphosphonite;6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphocin;6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl-dibenzo[d,g]-1,3,2-dioxaphosphocin;bis(2,4-di-tert-butyl-6-methylphenyl)methylphosphite; andbis(2,4-di-tert-butyl-6-methylphenyl)ethylphosphite.

(e) Hydroxylamines such as N,N-dibenzylhydroxylamine;N,N-diethylhydroxylamine; N,N-dioctylhydroxylamine;N,N-dilaurylhydroxylamine; N,N-ditetradecylhydroxylamine;N,N-dihexadecylhydroxylamine; N,N-dioctadecylhydroxylamine;N-hexadecyl-N-octadecyl-hydroxylamine;N-heptadecyl-N-octadecylhydroxylamine; and N,N-dialkylhydroxylaminederived from hydrogenated tallow fatty amines.

(f) Nitrones such as N-benzyl-alpha-phenyl nitrone; N-ethyl-alpha-methylnitrone; N-octyl-alpha-heptyl nitrone; N-lauryl-alpha-undecyl nitrone;N-tetradecyl-alpha-tridecyl nitrone; N-hexadecyl-alpha-pentadecylnitrone; N-octadecyl-alpha-heptadecyl nitrone;N-hexadecyl-alpha-heptadecyl nitrone; N-octadecyl-alpha-pentadecylnitrone; N-heptadecyl-alpha-heptadecyl nitrone;N-octadecyl-alpha-hexadecyl nitrone; and nitrones derived fromN,N-dialkylhydroxylamines prepared from hydrogenated tallow fattyamines.

(g) Thiosynergists such as dilauryl thiodipropionate and distearylthiodipropionate.

(h) Peroxide scavengers such as esters of β-thiodipropionic acid, forexample the lauryl, stearyl, myristyl or tridecyl esters;mercaptobenzimidazole or the zinc salt of 2-mercaptobenzimidazole; zincdibutyldithiocarbamate; dioctadecyl disulfide; and pentaerythritoltetrakis(β-dodecylmercapto)propionate.

(i) Polyamide stabilizers such as copper salts in combination withiodides and/or phosphorus compounds and salts of divalent manganese.

(j) Basic co-stabilizers such as melamine; polyvinylpyrrolidone;dicyandiamide; triallyl cyanurate; urea derivatives; hydrazinederivatives; amines; polyamides; polyurethanes; alkali metal salts andalkaline earth metal salts of higher fatty acids, for example calciumstearate, zinc stearate, magnesium behenate, magnesium stearate, sodiumricinoleate and potassium palmitate; antimony pyrocatecholate; and tinpyrocatecholate.

(k) Nucleating agents including inorganic substances such as talc andmetal oxides (e.g. titanium oxide or magnesium oxide) and phosphates,carbonates and sulfates of, preferably, alkaline earth metals; organiccompounds such as mono- or polycarboxylic acids and salts thereof, forexample 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid,sodium succinate and sodium benzoate; and polymeric compounds such asionic copolymers (e.g., ionomers).

(l) Fillers and reinforcing agents such as calcium carbonate; silicates;glass fibers; asbestos; talc; kaolin; mica; barium sulfate; metal oxidesand hydroxides; carbon black; graphite; wood flour and flours or fibersfrom other natural products; and synthetic fibers.

(m) Other additives such as plasticizers, lubricants, emulsifiers,pigments, rheological additives, catalysts, levelling assistants,optical brighteners, flameproofing agents, antistatic agents and blowingagents.

(n) Benzofuranones and indolinones such as those disclosed in U.S. Pat.Nos. 4,325,863, 4,338,244, 5,175,312, 5,216,052, 5,252,643,DE-A-4316611, DE-A-4316622, DE-A-4316876, EP-A-0589839 and EP-A-0591102;3-[4-(2-acetoxy-ethoxy)phenyl]-5,7-di-tert-butyl-benzofuran-2-one;5,7-di-tert-butyl-3-[4-(2-stearoyloxyethoxy)-phenyl]benzofuran-2-one;3,3′-bis[5,7-di-tert-butyl-3-(4-[2-hydroxyethoxy]phenyl)benzofuran-2-one];5,7-di-tert-butyl-3-(4-ethoxyphenyl)benzofuran-2-one;3-(4-acetoxy-3,5-dimethylphenyl)-5,7-di-tert-butyl-benzofuran-2-one;3-(3,5-dimethyl-4-pivaloyloxyphenyl)-5,7-di-tert-butyl-benzofuran-2-one;and 5,7-di-tert-butyl-3-(3,4-dimethylphenyl)-3H-benzofuran-2-one.

The novel benzocycle-substituted pyrimidines and triazines of thepresent invention can also be employed in multilayer systems. In suchsystems, a polymer composition having from about 0.1 to about 20% byweight and preferably a relatively high content of novel stabilizer, forexample, about 5-15% by weight, is applied in a thin film (e.g., about5-500 μm thick and, preferably, about 10-100 μm thick) to a shapedarticle made from a polymer containing little or no ultravioletstabilizers. Such composition may be applied at the same time as theshaping of the base structure, for example by coextrusion in a manneranalogous to that described in U.S. Pat. No. 4,948,666 (incorporated byreference herein for all purposes as if fully set forth). Alternatively,application can also be made to the ready-formed base structure, forexample by lamination with a film or by coating with a solution. Theouter layer or layers of the finished article have the function of a UVfilter, which protects the interior of the article from UV light. Theouter layer preferably contains about 0.1 to about 20%, preferably about1 to about 15%, and most preferably about 2 to about 10% by weight ofthe outer layer composition, of at least one of thebenzocycle-substituted pyrimidine or triazine compounds of the presentinvention.

The polymers stabilized in this way are notable for high weatheringresistance, especially for high resistance to UV light. This enablesthem to retain their mechanical properties, and their color surfaceproperties such as gloss and distinctness of image, for a long time evenwhen used outside. Moreover, due to the bondable nature of the presentlyclaimed triazine compounds, migration of these UV absorbers between thelayers of the multi-layer coatings can, under the appropriatecircumstances, be minimized.

In another embodiment of the present invention, the novel mixturescomprising compounds of the formula (I), (II), or (IV)-(IX) can be usedas stabilizers for coatings, for example for paints such as disclosed innumerous references (see, e.g., U.S. Pat. Nos. 4,619,956, 4,740,542,4,826,978, 4,962,142, 5,106,891, 5,198,498, 5,298,067, 5,322,868,5,354,794, 5,369,140, 5,420,204, 5,461,151, 5,476,937, EP-0434608 andEP-A-0444323). Of particular interest are coatings and paints for theautomobile industry. The invention therefore also relates to thosecompositions which are film-forming binders for coatings.

Such novel coating compositions comprise about 0.01 to about 20%,preferably about 0.01 to about 10%, and more preferably about 0.02 toabout 5% by weight of the binder of the coating composition of thepresently claimed benzocycle-substituted pyrimidines and triazines ofthe present invention.

Multilayer systems are possible here as well (such aselectrocoat/basecoat/clearcoat systems), where the concentration of thenovel stabilizer in one or more of the layers, and typically the outerlayer such as the clearcoat, can be relatively high, for example fromabout 0.01 to about 20%, preferably about 0.01 to about 10%, and morepreferably about 0.02 to about 5% by weight of binder.

The use of the novel stabilizer in coatings is accompanied by theadditional advantage that it prevents delamination, i.e. the flaking-offof the coating from the substrate. This advantage is particularlyimportant in the case of metallic substrates, including multilayersystems on metallic substrates, and particularly epoxy e-coated metallicsubstrates.

The binder can in principle be any binder which is customary inindustry, for example those described in Ullmann's Encyclopedia ofIndustrial Chemistry, 5th Edition, Vol. A18, pp. 368-426, VCH, Weinheim1991 which is incorporated herein by reference. In general, it is afilm-forming binder based on a thermoplastic or curable resin,predominantly on a curable resin. Examples of thermoplastic bindersinclude acrylics, polyesters, polyurethanes and PVC plastisols. Examplesof curable binders include functional alkyd, acrylic, polyester,phenolic, melamine, epoxy and polyurethane resins and mixtures thereof.

Such curable binders can be an ambient curable or a thermosettingbinder. Further, in some systems it may be advantageous to add a curingcatalyst to such systems. Suitable catalysts which accelerate curing ofthe binder are described, for example, in Ullmann's Encyclopedia ofIndustrial Chemistry, Vol. A18, p. 469, VCH Verlagsgesellschaft,Weinheim 1991. Preferred binders include those which comprise afunctional acrylate resin and a crosslinking agent.

A wide variety of binders may be employed in such coating systems.

Examples of suitable coating compositions containing specific bindersinclude but are not limited to:

1. paints based on ambient curable or thermosetting alkyd, acrylate,polyester, epoxy or melamine resins or mixtures of such resins, ifdesired with addition of a curing catalyst;

2. two-component polyurethane paints based on hydroxyl-containingacrylate, polyester or polyether resins and aliphatic or aromaticisocyanates, isocyanurates or polyisocyanates;

3. one-component polyurethane paints based on blocked isocyanates,isocyanurates or polyisocyanates which are deblocked during baking;

4. two-component paints based on (poly)ketimines and aliphatic oraromatic isocyanates, isocyanurates or polyisocyanates;

5. two-component paints based on (poly)ketimines and an unsaturatedacrylate resin or a polyacetoacetate resin or a methacrylamidoglycolatemethyl ester;

6. two-component paints based on carboxyl- or amino-containingpolyacrylates and polyepoxides;

7. two-component paints based on acrylate resins containing anhydridegroups and on a polyhydroxy or polyamino component;

8. two-component paints based on (poly)oxazolines and acrylate resinscontaining anhydride groups, or unsaturated acrylate resins, oraliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

9. two-component paints based on unsaturated polyacrylates andpolymalonates;

10. thermoplastic polyacrylate paints based on thermoplastic acrylateresins or externally crosslinking acrylate resins in combination withetherified melamine resins;

11. paint systems based on siloxane-modified or fluorine-modifiedacrylate resins.

In addition to the binder and novel benzocycle-substituted pyrimidinesand triazines of the present invention, the coating compositionaccording to the invention preferably further comprise one or moreadditional ultraviolet light absorbers, including but not limited tothose specifically listed above in section b. The additional UVabsorbers may be, for example, another tris-aryl-1,3,5-triazine, a2-hydroxyphenyl-2H-benzotriazole, a 2-hydroxybenzophenone, an ester ofan unsubstituted benzoic acid, an acrylate, an oxamide (oxanilide), orany combination of the above. Preferably, the additional UV absorber isa 2-hydroxyphenyl-2H-benzotriazole and the weight ratio of benzotriazoleto triazine is 4:1 to 1:4. More preferably, the weight ratio is 2:1 to1:2.

To achieve maximum light stability, it is of particular interest to addsterically hindered amines, examples of which are set out in theabove-mentioned section b(vi). The invention therefore also relates to acoating composition which, in addition to the binder, the novelbenzocycle-substituted pyrimidines and triazines and, optionally,additional UV absorbers, comprises a light stabilizer of the stericallyhindered amine type. The sterically hindered amine is employed in anamount of about 0.01 to 5% by weight based on the weight of the solidbinder, preferably about 0.02 to 2% by weight.

One specific example of such a sterically hindered amine is a2,2,6,6-tetramethyl piperazinone containing at least one group of theformula:

in which J is, for example, hydrogen, hydroxyl, alkyl (such as methyl),alkoxy (such as methoxy) or acyl.

More preferably the stabilizer is a 2,2,6,6-tetraalkylpiperidinederivative containing at least one group of the formula:

in which J is, for example, hydrogen, hydroxyl, alkyl (such as methyl),alkoxy (such as methoxy) or acyl.

Examples of tetraalkylpiperidine derivatives which can be used incombination with the present trisaryl-1,3,5-triazine compounds are givenin U.S. Pat. Nos. 4,314,933, 4,344,876, 4,426,471, 4,426,472, 4,619,956,5,004,770, 5,006,577, 5,064,883, 5,112,890, 5,124,378, 5,106,891,5,204,473, and 5,461,151, which are incorporated by reference herein forall purposes as if fully set forth. It is particularly expedient toemploy the following tetraalkylpiperidine derivatives, as well as theirN-alkyl, N-acyl, N-hydroxyl and N-alkoxy analogs (where not alreadyincluded in the following list):

bis(2,2,6,6-tetramethylpiperid-4-yl) succinate,

bis(2,2,6,6-tetramethylpiperid-4-yl) sebacate,

bis(1,2,2,6,6-pentamethylpiperid-4-yl) sebacate,

di(1,2,2,6,6-pentamethylpiperid-4-yl)butyl-(3,5-di-tert-butyl-4-hydroxybenzyl)malonate,

bis(1-octyloxy-2,2,6,6-tetramethylpiperid-4-yl) sebacate,tetra(2,2,6,6-tetramethylpiperid-4-yl) butane-1,2,3,4-tetracarboxylate,tetra(1,2,2,6,6-pentamethylpiperid-4-yl)butane-1,2,3,4-tetracarboxylate,2,2,4,4-tetramethyl-7-oxa-3,20-diaza-21-oxo-dispiro[5.1.11.2]heneicosane,and8-acetyl-3-dodecyl-1,3,8-triaza-7,7,9,9-tetramethylspiro[4.5]decane-2,4-dione.

Commercially available examples of these and other tetraalkylpipieridinederivatives include SANDUVOR® 3050, 3052, 3055, 3056, 3058, PR-31 andPR-32 (Clariant Corp.); TINUVIN® 079L, 123, 144, 292, 440L and 622LD(Ciba Specialty Chemicals); CHIMASORB® 119 and 944 (Ciba SpecialtyChemicals); and CYASORB® UV-3346, UV 3529, UV-3853, UV-500 and UV-516(Cytec Industries Inc.).

Apart from the binder, the benzocycle-substituted pyrimidine ortriazine, and, if used, the additional ultraviolet light absorber orstabilizer, the coating composition can also comprise furthercomponents, examples being solvents, pigments, dyes, plasticizers,stabilizers, thixotropic agents, drying catalysts and/or levelingagents. Examples of possible components are those described in many ofthe previously incorporated references as well as Ullmann's Encyclopediaof Industrial Chemistry, 5th Edition, Vol. A18, pp. 429-471, VCH,Weinheim 1991; and Calbo, Leonard J., ed., Handbook of CoatingsAdditives, New York:Marcel Dekker (1987).

Possible drying catalysts or curing catalysts are, for example,organometallic compounds, amines, acids, amino-containing resins and/orphosphines.

Examples of acid catalysts are mineral acids, aliphatic and aromaticsulfonic acids (e.g. p-toluene sulfonic acid, dinonylnaphthalenedisulfonic acid, dodecylbenzene sulfonic acid), oxalic acid, maleicacid, hexamic acid, phosphoric acid, alkyl phosphate esters, phthalicacid and acrylic acid copolymers.

Examples of organometallic compounds are metal carboxylates, especiallythose of the metals Pb, Mn, Co, Zn, Zr or Cu, or metal chelates,especially those of the metal Al, It or Zr, or organometallic compoundssuch as organotin compounds, for example. Examples of metal carboxylatesare the stearates of Pb, Mn or Zn, the octoates of Co, Zn or Cu, thenaphthenates of Mn and Co or the corresponding linoleates, resinates ortallates. Examples of metal chelates are the aluminum, titanium orzirconium chelates of acetylacetone, ethyl acetylacetate,salicylaldehyde, salicylaldoxime, o-hydroxyacetophenone or ethyltrifluoroacetylacetate and the alkoxides of these metals. Examples oforganotin compounds are dibutyltin oxide, dibutyltin dilaurate ordibutyltin dioctoate.

Examples of amine drying or curing catalysts are, in particular,tertiary amines, for example tributylamine, triethanolamine,N-methyldiethanolamine, N-dimethylethanolamine, N-ethylmorpholine,N-methylmorpholine or diazabicyclooctane (triethylenediamine) and saltsthereof. Further examples are quaternary ammonium salts, for exampletrimethylbenzylammonium chloride. Amino-containing resins aresimultaneously binder and curing catalyst. Examples thereof areamino-containing acrylate copolymers.

The curing catalyst used can also be a phosphine, for exampletriphenylphosphine.

Another type of curing catalyst is a peroxide which can be used, forexample, to cure a gel coating for a fiberglass article.

The novel coating compositions can also be radiation-curable coatingcompositions. In this case, the binder essentially comprises monomericor oligomeric compounds containing ethylenically unsaturated bonds,which after application are cured by actinic radiation, i.e. convertedinto a crosslinked, high molecular weight form. Where the system isUV-curing, it generally contains a photoinitiator as well. Correspondingsystems are described in the above-mentioned publication Ullmann'sEncyclopedia of Industrial Chemistry, 5th Edition, Vol. A18, pages451-453. In radiation-curable coating compositions, the novelstabilizers can also be employed without the addition of stericallyhindered amines.

The novel coating compositions according to the invention can be appliedto any desired substrates, for example to metal, wood, plastic,fiberglass or ceramic materials. The coating compositions can bepigmented mono-coats or multi-layer (primer/basecoat/clearcoat) systemstypical of automotive finishes. In the latter case, the novel coatingcomposition can be used for either the base coat, or clear coat, or forboth layers. If the topcoat of an automotive finish comprises twolayers, of which the lower layer is pigmented and the upper layer is notpigmented, the novel coating composition can be used for either theupper or the lower layer or for both layers, but preferably for theupper topcoat layer.

The novel coating compositions can be applied to the substrates by thecustomary methods, for example by brushing, spraying, pouring, dippingor electrophoresis; see also Ullmann's Encyclopedia of IndustrialChemistry, 5th Edition, Vol. A18, pp. 491-500.

Depending on the binder system, the coatings can be cured at roomtemperature or by heating. Thermosetting coatings are preferably curedat 50-150° C. and, in the case of powder coatings, even at highertemperatures.

The coatings obtained in accordance with the invention have excellentresistance to the damaging effects of light, oxygen and heat; particularmention should be made of the good light stability and weatheringresistance of the coatings thus obtained, for example paints.

The invention therefore also relates to a coating, in particular apaint, which has been stabilized against the damaging effects of light,oxygen and heat by a content of the compound of the formula (I), (II),or (IV)-(IX), according to the invention. The paint can be a pigmentedmono-coat which comprises a film-forming binder and an organic pigmentor dye, an inorganic pigment, a metallic pigment, or a mixture thereof.The paint may also be a composition which comprises a primer in adhesionto a metal or plastic substrate; a pigmented basecoat that is inadhesion to the primer and which comprises a film-forming binder and anorganic pigment or dye, an inorganic pigment, a metallic pigment, or amixture thereof; and a clear coat that is in adhesion to the base coatand which comprises a film-forming binder and optionally a transparentpigment. One especially preferred use is a paint which is a cleartopcoat for automobile original equipment manufacture (OEM) and/orrefinish applications.

The invention furthermore relates to a process for stabilizing a coatingbased on polymers against damage by light, oxygen and/or heat, whichcomprises mixing with the coating composition a mixture comprising acompound of a benzocycle-substituted pyrimidine or triazine and to theuse of mixtures comprising benzocycle-substituted pyrimidine or triazinecompound in coating compositions as stabilizers against damage by light,oxygen and/or heat.

The coating compositions can comprise an organic solvent or solventmixture in which the binder is soluble. The coating composition canotherwise be an aqueous solution or dispersion. The vehicle can also bea mixture of organic solvent and water. The coating composition maybe ahigh-solids paint or can be solvent-free (e.g. a powder coatingmaterial).

The pigments can be inorganic, organic or metallic pigments. The novelcoating compositions preferably contain no pigments and are used as aclearcoat.

Likewise preferred is the use of the coating composition as a topcoatfor applications in the automobile industry, especially as a pigmentedor unpigmented topcoat of the paint finish. Its use for underlyingcoats, however, is also possible.

The benzocycle-substituted pyrimidine or triazines of this invention maybe applied topically by polishing a surface with a compositioncomprising the benzocycle-substituted pyrimidine or triazines and aninert carrier such as solvent, petroleum jelly, silicone oil in wateremulsions, or automotive paint wax, e.g. Carnauba wax. These topicaltreatment compositions may be used to stabilize coating films, fabrics,leather, vinyl and other plastics and wood.

Preference is also given to the use of the novel benzocycle-substitutedpyrimidine or triazine compounds in photographic materials as stabilizeragainst damage by light, especially by UV light. The invention thereforealso relates to a photographic material comprising anbenzocycle-substituted pyrimidine or triazine compound.

The compounds according to the invention can be used for photosensitivematerials of all kinds. For example, they can be employed for colorpaper, color reversal paper, direct-positive color material, colornegative film, color positive film, color reversal film and othermaterials. They are preferably used, inter alia, for photosensitivecolor material which comprises a reversal substrate or which formspositives.

Furthermore, the novel compounds can be combined with other UVabsorbers, especially those which are dispersible in aqueous gelatin,for example with hydroxyphenylbenzotriazoles (cf. for example U.S. Pat.Nos. 4,853,471, 4,973,702, 4,921,966 and 4,973,701), benzophenones,oxanilides, cyanoacrylates, salicylates, or acrylonitriles orthiazolines. In this context it is advantageous to employ these further,oil-dissolved UV absorbers in the photographic material in layers otherthan those comprising the novel UV absorbers.

The present invention also encompasses compositions containing one ormore binders. In particular, the binder may comprise an alkyd, acrylic,polyester, phenolic, melamine, epoxy or polyurethane resin, or blendsthereof. Examples of such binders include, but are not limited to:

(a) cold- or hot-crosslinkable alkyd, acrylate, polyester, epoxy ormelamine resins or mixtures of such resins;

(b) a two-component polyurethane system comprising hydroxyl-containingacrylate, polyester or polyether resins and aliphatic or aromaticisocyanates, isocyanurates or polyisocyanates;

(c) a one-component polyurethane system comprising blocked isocyanates,isocyanurates or polyisocyanates which are deblocked during baking;

(d) a two-component system comprising (poly)ketimines and aliphatic oraromatic isocyanates, isocyanurates or polyisocyanates;

(e) a two-component system comprising (poly)ketimines and an unsaturatedacrylate resin or a polyacetoacetate resin or a methacrylamidoglycolatemethyl ester;

(f) a two-component system comprising carboxyl- or amino-containingpolyacrylates and polyepoxides;

(g) a two-component system comprising acrylate resins containinganhydride groups and on a polyhydroxy or polyamino component;

(h) a two-component system comprising (poly)oxazolines and acrylateresins containing anhydride groups, or unsaturated acrylate resins, oraliphatic or aromatic isocyanates, isocyanurates or polyisocyanates;

(i) a two-component system comprising unsaturated polyacrylates andpolymalonates;

(j) a thermoplastic polyacrylate system comprising thermoplasticacrylate resins or externally crosslinking acrylate resins incombination with etherified melamine resins; and

(k) a system comprising siloxane-modified or fluorine-modified acrylateresins. Such binder-containing compositions may further comprise acuring catalyst, or an organic solvent, and may be radiation-curable. Inparticular, such compositions may serve as coating compositions.

In particular, it is possible successfully to stabilize photographicmaterials similar to those described in U.S. Pat. No. 4,518,686.

The invention therefore additionally relates to a photographic materialcomprising, on support, a blue-sensitive, a green-sensitive and/or ared-sensitive silver-halide emulsion layer and, if desired, a protectivelayer, with a layer comprising a UV absorber being arranged above theuppermost silver-halide emulsion layer, wherein the UV absorber is abenzocycle-substituted pyrimidine or triazine compound.

Preference is additionally given to photographic materials which have alayer comprising a compound of the formula (I), (II), or (IV)-(IX) abovethe uppermost silver-halide emulsion layer and/or between the green- andred-sensitive silver-halide emulsion layers.

Furthermore, it may be advantageous for all or some of the said layerswhich can comprise a UV absorber to have a UV absorber mixture and/or afurther UV absorber which is dispersible in aqueous gelatin, but acompound of the formula (I), (II), or (IV)-(IX) must be present at leastin one layer.

The novel material preferably has gelatin interlayers between thesilver-halide emulsion layers.

Preference is given to photographic materials in which the silver halidein the blue-sensitive, green-sensitive and/or red-sensitive layer issilver chloride bromide comprising at least 90 mol % of silver chloride.

The compounds of the formula (I), (II), or (IV)-(IX), which are used inaccordance with the invention, can be incorporated, alone or togetherwith the color coupler and, if used, further additives, into the colorphotographic materials by dissolving the compounds beforehand inhigh-boiling organic solvents. It is preferred to use solvents whichboil at higher than 160° C. Typical examples of such solvents are theesters of phthalic acid, phosphoric acid, citric acid, benzoic acid orof fatty acids, or alkylamides and phenols.

Preferred color couplers for use in the compositions of the invention,examples of such compounds, further additives such as color castinhibitors, DIR couplers and further light stabilizers, such as UVabsorbers, phenols, phosphorus (III) compounds, organometalliccomplexes, hydroquinones and hydroquinone ethers, and more precisedetails on the structure of various photographic materials, can befound, for example, in the publications EP-A-0531258 and EP-A-0520938and in the literature cited therein.

Film

The invention also relates to a process for the stabilization ofpolyolefin or polyolefin copolymer films for agricultural applications,especially greenhouse applications, this polyolefin or polyolefincopolymer film having improved light stability and pesticide resistance,comprising incorporation of at least one benzocycle-substitutedpyrimidine or triazine UV absorbers of the present invention, stericallyhindered amines and metal oxides of hydroxides selected from the oxidesof zinc, aluminum, calcium, and magnesium and hydroxides of zinc,aluminum, and calcium into the polyolefin or polyolefin copolymer.

A further subject of the invention is a greenhouse, characterized inthat it is covered by a polyolefin or polyolefin copolymer film havingimproved light stability and pesticide resistance and stabilized with aat least one benzocycle-substituted pyrimidine or triazine UV absorbersof the present invention, sterically hindered amines and metal oxides ofhydroxides selected from the oxides of zinc, aluminum, calcium, andmagnesium and hydroxides of zinc, aluminum, and calcium.

Another subject of the invention is a process for stabilizing apolyolefin or polyolefin copolymer greenhouse film against detrimentaleffects of pesticides and light, oxygen and/or heat, which processcomprises incorporation of at least one benzocycle-substitutedpyrimidine or triazine UV absorbers of the present invention, stericallyhindered amines and metal oxides of hydroxides selected from the oxidesof zinc, aluminum, calcium, and magnesium and hydroxides of zinc,aluminum, and calcium into said greenhouse film.

Further subjects of the invention are the use of a polyolefin copolymerfilm stabilized with at least one benzocycle-substituted pyrimidine ortriazine UV absorbers of the present invention, sterically hinderedamines and metal oxides of hydroxides selected from the oxides of zinc,aluminum, calcium, and magnesium and hydroxides of zinc, aluminum, andcalcium for the stabilization of polyolefin or polyolefin copolymerfilms in contact with pesticides against photodegradation and damage bypesticides.

To form a film, forcing a quantity of the said melted compositionthrough a film die, such as a flat film die or a circular blown filmdie, and forming a film therefrom. In the case where the composition isused to form a film therefrom, it is contemplated that the films may beunoriented, or may be subjected to a conventional operation to impart adegree of orientation on the film. Such a film may be oriented in onedirection, such as in the machine direction, such as in the “machinedirection” and/or the “transverse direction”, or may be oriented in bothdirections, or “biaxially” oriented.

The present invention is also suitable for sheet applications.

The benzocycle-substituted pyrimidine or triazine compounds of theformula (I), (II), or (IV)-(IX) are suitable for the photochemicalstabilization of undyed, dyed or printed fiber materials comprising forexample, silk, leather, wool, polyamide or polyurethanes and especiallycellulose-containing fiber materials of all kinds. Examples of suchfiber materials are the natural cellulose fibers, such as cotton, linen,jute and hemp and also viscose staple fiber and regenerated cellulose.Preferred textile fiber materials are those of cotton. The triazine andpyrimidine compounds of the present invention are also suitable for thephotochemical stabilization of hydroxyl-containing fibers in blendfabrics, for example blends of cotton with polyester fibers or polyamidefibers. A further preferred area of application relates to the blockingor reduction of the UV radiation which passes through theabove-mentioned textile materials (UV cutting) and the heightened sunprotection which textile materials finished with a novel compound offerto the human skin.

To this end, one or a number of different compounds of the formula (I),(II), or (IV)-(IX) are applied to the textile fiber material by one ofthe customary dyeing methods, advantageously in a quantity of 0.01 to 5%by weight, preferably 0.1 to 3% by weight and, in particular, from 0.25to 2% by weight, based on the weight of the fiber material.

The benzocycle-substituted pyrimidine or triazine compounds can beapplied to the fiber material in various ways and fixed on the fiber,especially in the form of aqueous dispersions or printing pastes.

The textile fiber materials finished with the novel compounds of theformula (I), (II), or (IV)-(IX) possess improved protection againstphotochemical breakdown of the fiber and yellowing phenomena and, in thecase of dyed fibre material, are of enhanced (hot) light fastness.Particular emphasis should be drawn to the greatly improvedphotoprotective effect of the treated textile fiber material and, inparticular, the good protective effect with respect to short-wave UV-Brays. This is manifested by the fact that the textile fiber materialfinished with an benzocycle-substituted pyrimidine or triazine compoundhas, relative to untreated fabric, a greatly increased sun protectionfactor (SPF).

The sun protection factor is defined as the quotient of the dose of UVradiation which damages protected skin to that which damages unprotectedskin. Accordingly, a sun protection factor is also a measure of theextent to which untreated fiber materials and fiber materials treatedwith a novel compound of the formula (I), (II), or (IV)-(IX) arepermeable to UV radiation. The determination of the sun protectionfactor of textile fiber materials is explained, for example, inWO94/04515 or in J. Soc. Cosmet. Chem. 40, 127-133 (1989) and can becarried out analogously thereto.

Yet another use of the UV absorbers according to the invention is in thestabilization of intra-ocular and contact lenses.

The inventive UV absorbers are suitable as photoprotective agents incosmetic preparations. The invention additionally relates, therefore, toa cosmetic preparation comprising at least one benzocycle-substitutedpyrimidine or triazine compound and cosmetically acceptable carriers orauxiliaries.

The novel cosmetic composition contains from 0.1 to 15% by weight,preferably from 0.5 to 10% by weight, based on the overall weight of thecomposition, of a benzocycle-substituted pyrimidine or triazine UVabsorber and a cosmetically acceptable auxiliary.

The cosmetic composition can be prepared by physically mixing the novelUV absorber with the auxiliary by means of customary methods, forexample by simply stirring together the two materials.

The cosmetic preparation according to the invention can be formulated asa water-in-oil or oil-in-water emulsion, as an oil-in-oil alcohollotion, as a vesicular dispersion of an ionic or nonionic amphiphiliclipid, as a gel, solid stick or as an aerosol formulation.

As a water-in-oil or oil-in-water emulsion, the cosmetically acceptableauxiliary preferably contains from 5 to 50% of an oily phase, from 5 to20% of an emulsifier and from 30 to 90% water. The oil phase cancomprise any oil which is suitable for cosmetic formulations, e.g., oneor more hydrocarbon oils, a wax, a natural oil, a silicone oil, a fattyacid ester or a fatty alcohol. Preferred mono- or polyols are ethanol,isopropanol, propylene glycol, hexylene glycol, glycerol and sorbitol.

For these cosmetic formulations, it is possible to use anyconventionally employed emulsifier, e.g., one or more ethoxylated estersof naturally occurring derivatives, i.e., polyethoxylated esters ofhydrogenated castor oil; or a silicone oil emulsifier such as siliconepolyol; an unmodified or ethoxylated fatty acid soap; an ethoxylatedfatty alcohol; an unmodified or ethoxylated sorbitan ester; anethoxylated fatty acid; or an ethoxylated glyceride.

The cosmetic formulation can also comprise further components, forexample emollients, emulsion stabilizers, skin moisteners, tanningaccelerators, thickeners such as xanthan, moisture retention agents suchas glycerol, preservatives, or fragrances and colorants.

The novel cosmetic formulations are notable for good protection of humanskin against the damaging effect of sunlight while at the same timeproviding for reliable tanning of the skin.

The invention will now be illustrated by the following examples. Theexamples are not intended to be limiting of the scope of the presentinvention. In conjunction with the general and detailed descriptionsabove, the examples provide further understanding of the presentinvention.

EXAMPLES

Examples and reaction schemes for producing specific examples ofbenzocycle substituted triazines in accordance with the invention areprovided below. While the following examples illustrate preparationswith one or more tetralin benzocyles, one of ordinary skill willunderstand that these reactions may also be carried out with any of avariety of other benzocycles, where when necessary, reactivesubstituents on such other benzocycles are protected in accordance withprocedures and reagents well known and understood by those of ordinaryskill.

Preparative Examples Example 1

Reaction of Cyanuric Chloride with Tetralin: Use of Tetralin as Solvent

To a reaction flask equipped with a reflux condenser, an argon inlet, amagnetic stirring bar and a glass stopper was added 100 mL of tetralinand 9.2 g of cyanuric chloride. To the resulting solution was added 10 gof anhydrous AlCl₃ over a period of 10 minutes at 0° C. After theaddition was over, the reaction mixture was heated in an oil bath at 40°C. for 16 hours. The heating was discontinued and the reaction mixturewas cooled in an ice bath and treated with ice-cold water. The reactionmixture was then extracted with methylene chloride and the organic layerdried over anhydrous sodium sulfate and concentrated to removevolatiles. The residue was treated with methanol affording a precipitatewhich was filtered, washed with methanol and dried to give 12.4 g of theproduct. The NMR and mass analysis of the product showed it to consistof a mixture of monotetralin-bischloro-triazine (Compound A),bistetralin-monochloro-triazine (Compound B) and tristetralin-triazine(Compound C).

Example 1 Alternate Procedure

Use of Monochlorobenzene as Solvent

A mixture of 47.7 g (0.256 mole) of cyanuric chloride and 67.6 g (0.507mol) of aluminum chloride in 360 mL of chlorobenzene under nitrogen washeated to 40° C. Tetralin (68 mL, 0.500 mole) was added over the courseof two hr. During this time the temperature increased to 50° C. Thetemperature was maintained at 50° C. until an exotherm occurred.

After the exotherm had subsided, 200 mL of 10% aqueous HCl was addeddrop-wise such that the temperature was maintained below 50° C. Theresulting mixture was filtered. The aqueous layer from the filtrate wasextracted with methylene chloride. The combined organic layers werewashed with water, dried over anhydrous magnesium sulfate, and treatedwith activated carbon. After filtration, the filtrate was concentratedin vacuo. The residue was taken up in 300 mL of tetrahydrofuran, andcooled to 0° C. The precipitate was removed by filtration. The filtratewas concentrated in vacuo to give an oil which slowly crystallized to adark yellow to brown solid, which contained P-4036 (50-70 area % byHPLC) plus tris-tetralin triazine and unreacted cyanuric chloride.

Example 2 Bistetralin-monoresorcinol-triazine (Compound D)

A mixture of 132.3 g of the product of Example 1 Alternate Procedure(Compound B) and 38.7 g of resorcinol in 300 mL of chlorobenzene washeated to 60° C. Aluminum chloride (61.0 g) was added over a 2 hr.during which time the temperature increased to 80° C. The mixture hasheld at 80° C. for an additional 2 hr.

After cooling to 60° C., the reaction mixture was poured into 400 mL ofice water. The mixture was concentrated in vacuo. The residue wastriturated with 400 mL of water, and the resulting slurry was filtered.The solid was air-dried and then dried in vacuo. A Soxhlet extraction ofthe solid was done with refluxing chloroform. A solid precipitated fromthe chloroform extract. The solid was filtered, washed with coldchloroform, and dried to give Compound D as a light yellow powderin >92% purity by HPLC.

Example 2 Alternate Procedure

To a stirred suspension of 40 g cyanuric chloride in 544 mLchlorobenzene maintained at ice bath temperature under nitrogen wasadded 87 g of aluminum chloride. Concentrated hydrochloric acid (4.34mL) was added over 10 min during which the reaction temperature was keptbelow 5° C. The reaction mixture was stirred at between about 0° C. toabout 5° C. for an additional 10 min, and then cooled to −10° C.Tetralin (56 mL) was added at −10° C. over 2 hr. The reaction mixturewas then stirred at −10° C. for 2 hr, warmed to 0° C., and stirred for 1hr.

The reaction mixture was heated to 40° C. and 26.3 g of resorcinol wasadded over 10 min. The mixture was heated to 80° C. and stirred for 2hr. Compound D was isolated according to the procedure of Example 3.

Example 3 Bistetralin-(monoresorcinol-4-O-octyl)-triazine derivative(Compound E)

A mixture of 400 mg of the product of Example 2 (Compound D), 1.38 g ofanhydrous potassium carbonate, 0.2 mL of 1-iodooctane and 10 mL ofacetone was heated to reflux for 24 hours. The reaction mixture was thencooled to room temperature and diluted with methylene chloride. Theresulting mixture was filtered through Celite, and concentrated todryness to give 422 mg of a crude product. The crude product waspurified by column chromatography over silica gel to give a purecompound which was identified to be thebistetralin-(monoresorcinol-4-O-octyl)-triazine derivative (Compound E)by NMR and mass spectra.

Example 4 Monotetralin-bischloro-triazine (Compound F)

A 3-necked, one liter flask was charged with 48 g of anhydrous aluminumchloride, 56.11 g of cyanuric chloride and 240 mL of chlorobenzene. Theapparatus was purged with nitrogen and the mixture was heated to 65° C.

Neat tetralin (60 mL) was added dropwise to the solution at a constantrate of about 1.3 mL per minute such that all the tetralin was added in45 minutes. The temperature was maintained between 63 and 68° C. duringthis period. As the addition of tetralin proceeded, the solution becamered-black in color. After the addition was complete, the temperature wasmaintained at 65-70° C. for an additional 60 min. The mixture was thenallowed to cool to about 50° C.

A mixture of 20 mL of concentrated aqueous HCl and 180 mL of water wasadded through the dropping funnel. During the addition the mixture wascooled with an ice bath. The aqueous acid was added dropwise at leastkeeping the temperature between 45 and 50° C., and then more rapidly asthe exothermic reaction lessened. The entire mixture was diluted with300 mL of methylene chloride, and the aqueous layer was removed. Theorganic layer was washed twice with water and then dried over anhydrousmagnesium sulfate.

The dried organic mixture was then filtered to remove magnesium sulfateand concentrated on a rotary evaporator. After cooling, about 300 mL ofhexanes was added giving a white precipitate. This was filtered andwashed with hexanes to give, after drying in vacuo, the desired product(Compound F) in 96% purity by HPLC analysis.

Example 5 Monotetralin-bisresorcinol-triazine (Compound G)

To a 3-necked 250-mL round bottomed flask was charged with 14.0 g ofmonotetralin-bischloro-triazine (Compound F), 11.56 g of resorcinol, and130 mL of chlorobenzene and then purged with nitrogen. Into the solidsaddition funnel was placed 18.76 g of anhydrous aluminum chloride. Thesolution was heated to 49° C. and addition of aluminum chloride wasbegun in portions. The aluminum chloride was added over the course oftwo hours and the temperature allowed to slowly climb to 65° C. Thereaction mixture was then heated to 90-95° C. and held in that range for3 hours. The mixture was a dark red slurry at this point.

At the end of the reaction period, the heat was removed and thetemperature allowed to fall to about 60° C. The attachments were thenremoved from the reaction flask and the mixture was poured into 200 mLof cold water. The mixture was shaken, discharging the red color andleaving a yellow emulsion. When this had cooled completely, it wastransferred to a round bottomed task and the chlorobenzene-waterazeotrope was removed on a rotary evaporator until no furtherchlorobenzene was observed in the condensate. The resultant light yellowslurry was filtered, washed with water and dried in vacuo to give thedesired product (Compound G).

Example 6 Preparation of Compounds H and I

A mixture of 4.27 g of Compound G, 5.28 g of 1-iodooctane, 6.9 g ofanhydrous potassium carbonate, 0.5 g of Aliquat 336 and 50 mL of acetonewas heated to reflux for 20 hr. At this stage additional 1 mL of1-iodooctane and 3.5 g of anhydrous potassium carbonate were added andthe refluxing was continued for an additional 8 hr. A TLC analysis atthis stage showed almost complete disappearance of Compound G andformation of two new products. The reaction mixture was allowed to coolto room temperature, diluted with methylene chloride and filteredthrough Celite. The filtrate was concentrated under reduced pressure togive a crude product which consisted of compounds H and I as analyzed byNMR and mass spectra. The mixture is separable by column chromatographyover silica gel.

Example 7 Preparation of 4-(2-hydoxyethyl)ether ofBis-Tetralin-mono-Resorcinol Triazine (Compound J)

A mixture of 10.0 g of bis-tetralin-mono-resorcinol triazine (CompoundD), 130 mL of DMF, 2.6 g of anhydrous sodium carbonate, 0.25 g ofpotassium iodide, 0.88 g of PEG-400 (polyethylene glycol), and 7.5 g of2-chloroethanol was heated to 120° C. for 15 hr. After the first 9 hr,an additional 2.5 g of 2-chloroethanol was added and heating wascontinued. After completion of the reaction, the mixture was poured into300 mL of ice water. The precipitated solids were filtered, washed withwater, and dried. HPLC and NMR analyses indicated that Compound J wasobtained in >90% purity.

Example 8 Preparation of 4-(6-hydroxyhexyl)ether ofBis-Tetralin-mono-Resorcinol Triazine (Compound K)

A mixture of 10 g of bis-tetralin-mono-resorcinol triazine (Compound D,0.02 mole) and 80 mL of MIBK was heated to 90° C. Sodium hydroxide 1.0 g(0.031 mole) was slowly added, resulting in a nearly clear solution.Then 0.25 g (0.0015 mole) of potassium iodide and 0.88 g of PEG-400(polyethylene glycol, approx. 0.0022 mole) were added. After thesolution again became clear, 5.7 g (0.031 mole) of 6-chlorohexanol wereadded. The mixture was heated at 107-111° C. for 18 hr. The mixture wasthen washed with 1 N HCl and with water. The resulting solution wasdried over magnesium sulfate, filtered and cooled to 0° C. The resultingpale yellow solid was filtered, dried. HPLC and NMR analyses indicatedthat the Compound K was obtained in >90% purity.

Example 9 Preparation of 4-Lauroyl Ester Derivative ofBis-Tetralin-mono-Resorcinol Triazine (Compound L)

To a mixture of 20 g of Compound D and 80 mL of ortho-dichlorobenzenewere added 11.0 mL of lauroyl chloride (Aldrich) and 10 mL ofortho-dichlorobenzene. The stirred mixture was heated at 150° C. for 9hr. The mixture was then cooled to 100° C. and 200 mL of ethanol wereadded. The resulting precipitate was filtered, washed with ethanol, andallowed to air affording 21.3 g of Compound L as a pale yellow solid.

The solid was dissolved in 50 mL of hot toluene. The slurry was warmedin a water bath until all of the solid dissolved. Methanol (300 mL) wasadded to the mixture maintained at reflux temperature. The solution wasthen cooled to room temperature. The resulting solid was filtered,washed with several portions of methanol, and dried in vacuo to give20.25 g of the title compound as a pale yellow solid.

Example 10 Preparation of 4-Hexanoyl Ester Derivative ofBis-Tetralin-mono-Resorcinol Triazine (Compound M)

To a mixture of 20 g of Compound D and 80 mL of ortho-dichlorobenzenewere added 8 mL of hexanoyl chloride (Aldrich) and 10 mL ofortho-dichlorobenzene. The stirred mixture was heated at 150° C. for12.5 hr. The product was isolated by the procedure of Example 9 to give14.1 g of the Compound M as a pale yellow solid.

Example 11 Preparation of 4-Octanoyl Ester Derivative ofBis-Tetralin-mono-Resorcinol Triazine (Compound N)

To a mixture of 20 g of Compound D and 80 mL of ortho-dichlorobenzenewere added 8 mL of octanoyl chloride (Aldrich) and 10 mL ofortho-dichlorobenzene. The stirred mixture was heated at 150° C. for23.5 hr. The product was isolated by the procedure of Example 2 to give17.8 g of the Compound N as a pale yellow solid.

Example 12 4-(2-Ethylhexanoyl) Ester Derivative ofBis-Tetralin-mono-Resorcinol Triazine (Compound O)

To a mixture of 20 g of Compound D and 80 mL of ortho-dichlorobenzenewere added 8 mL of 2-ethylhexanoyl chloride (Aldrich) and 10 mL ofortho-dichlorobenzene. The stirred mixture was heated at 150° C. for 20hr. The mixture was then cooled to 100° C. and 200 mL of ethanol wasadded. Upon cooling to 0° C. overnight an oil precipitated. Thesupernatant was decanted off. The oil was dissolved in a refluxinghexanes-toluene mixture, and then cooled to 0° C. The resulting solidwas filtered, washed with methanol, and air dried to give 21.4 g of apale yellow solid. The solid was recrystallized from hexanes-toluene,filtered, washed with methanol, and dried in vacuo to give 15.8 g ofCompound O as a pale yellow solid.

Example 13 4-(3,5,5-trimethylhexanoyl) Ester Derivative ofBis-Tetralin-mono-Resorcinol Triazine (Compound P)

To a mixture of 20 g of Compound D and 80 mL of ortho-dichlorobenzenewere added 9 mL of 3,5,5-trimethylhexanoyl chloride (Aldrich) and 10 mLof ortho-dichlorobenzene. The stirred mixture was heated at 150° C. for7 hr. The mixture was then cooled to 100° C. and 200 mL of ethanol wasadded. Upon cooling to 0° C. overnight, an oil precipitated. Thesupernatant was decanted off. The oil was washed with five 150 mLportions of methanol and dried in vacuo. The resulting glass wasrecrystallized twice from hexanes to give 13.1 g of the Compound P as apale yellow solid.

Example 14 Preparation of2-(2-hydroxy-4-ethoxycarbonylmethoxyphenyl)-4,6-bis(tretralin)-1,3,5-triazine(Compound Q)

To a mixture of 9 g of Compound D, 6.9 g of anhydrous potassiumcarbonate, 0.3 g of potassium iodide and 50 mL of acetone was added 2.4mL (2.7 g) of ethyl chloroacetate. The mixture was stirred at reflux forsix hours. HPLC analysis indicated full conversion of Compound D. Aftercooling, the mixture was diluted with 100 mL of methylene chloride andfiltered through a bed of diatomaceous earth, which was washed with anadditional 50 mL of methylene chloride. The combined filtrates wereconcentrated in vacuo. The product was recrystallized from ethyl acetateand dried in vacuo to give 8.4 g of Compound Q as a near white solid in94% purity (HPLC area % at 290 nm). The structure was verified by ¹³Cand ¹H-NMR spectroscopy.

Example 15 Preparation of2-[2-hydroxy-4-(N-(n-butyl)-N-(2-hydroxyethyl)-methanamidooxy)phenyl]-4,6-bis(tetralin)-1,3,5-triazine)(Compound R)

A mixture of 5 g of Compound Q, 1.66 g of butyl ethanolamine, 0.12 g of4-dimethylaminopyridine, and 30 mL of xylenes was stirred at reflux.After 26 hr, 2 g of butyl ethanolamine was added. After 48 hr, HPLCanalysis showed 99.5% conversion of Compound P (area % at 290 nm). Themixture was allowed to cool. The precipitated solids were diluted with175 mL of hexanes and stirred for 3 hr. The mixture was filtered and thecollected solid was air dried. The solid was stirred with 150 mL ofmethanol for several hours, filtered, washed with methanol, and dried invacuo to give 5 g of Compound R as a white solid in 96% purity (HPLCarea % at 290 nm). The structure was verified by ¹³C and ¹H-NMRspectroscopy.

Example 16 Preparation of bis-tetralin-mono-resorcinol triazine4-O-propanesulfonate ester (Compound S)

To a stirred mixture of 11.6 g of Compound D, 9 g of anhydrous potassiumcarbonate, and 100 mL of tetrahydrofuran (THF), cooled to 4° C. wasadded a solution of 3.15 mL of propanesulfonyl chloride in 30 mL of THFover 22 min. The resulting mixture was stirred for 40 hr at roomtemperature. An additional 1 mL of propanesulfonyl chloride was added,and the mixture was stirred for 24 hr. HPLC analysis showed completeconversion of starting material. The solids were removed by filtrationand the product was crystallized from the filtrate. The filtered solidswere extracted with chloroform, and the chloroform was removed in vacuoto afford additional product. The combined yield was 8.5 g.Recrystallization from ethyl acetate afforded Compound S in 99% purityas determined by HPLC (area % at 290 nm). The structure was verified byIR, ¹³C, and ¹H-NMR spectroscopy.

Example 17 Preparation of bis-tetralin-mono-resorcinol triazine4-O-phenylsulfonate ester (Compound T)

To a mixture of 15 g of Compound D, 13.8 g of anhydrous potassiumcarbonate and 100 mL of tetrahydrofuran, cooled to 4° C., was added asolution of 5.2 mL (7.1 g) of benzenesulfonyl chloride in 30 mL of THFover 37 minutes. The resulting mixture was allowed to warm to roomtemperature and stirred for 19 hr. An additional 1 mL of benzenesulfonylchloride was added, and the mixture was stirred for 3 hr. Methanol (5mL) was added. The mixture was filtered, and the solids washed with THF.

The product was crystallized from the combined filtrates, filtered, anddried. Compound T (11.3 g) was obtained as a white solid byrecrystallization from chloroform/hexanes (1:3 v/v). HPLC analysisshowed 99% purity (area at 290 nm). The structure was verified by ¹³Cand ¹H-NMR spectroscopy.

Example 18 Preparation ofmonotetralin-monoresorcinol-monochloro-1,3,5-triazine (Compound U)

To a stirring mixture of 2.8 g of monotetralin-bischloro-1,3,5-triazine(Compound F), 1 g of resorcinol, and 25 mL of chlorobenzene was added1.34 g of aluminum chloride at ice-bath temperature. The reactionmixture was allowed to warm to 15° C. and stirred for 3 hr. The reactionmixture was then allowed to warm to room temperature and stirred for 20hr. The reaction mixture was quenched with ice-cold 2% aqueoushydrochloric acid. A precipitate formed, whcih was collected byfiltration, washed with water, and dried. The precipitate was analyzedby thin layer chromatography (TLC), HPLC, and mass spectroscopy, whichidentified Compound U as the major product.

Example 19 Preparation of a hindered phenol adduct ofbistetralin-monoresorcinol-1,3,5-triazine (Compound V)

To a stirring mixture of 2.25 g of compound D, 2.76 g of anhydrouspotassium carbonate, and 50 mL of acetone was added 1.24 g of3-chloromethyl-2,4-dimethyl-6-tert-butylphenol, 150 mg of sodium iodideand 250 mg of Aliquat® 336 (triscaprylmethylammonium chloride). Thereaction mixture was heated to reflux for 3 hr. No starting material andonly one major product was detected using TLC and HPLC analysis. Thereaction mixture was allowed to cool to room temperature, diluted with50 mL of methylene chloride, and filtered through Celite® brand filteragent. The filtrate was concentrated under reduced pressure. The residuewas dissolve in 100 mL of methylene chloride, washed with water, driedover anhydrous sodium sulfate, and concentrated to dryness to giveCompound V, which was analyzed by mass spectroscopy.

Example 20 Preparation of hindered phenol adducts ofmonotetralin-bisresorcinol-1,3,5-triazine (Compounds W and X)

To a stirring mixture of 2.14 g of Compound G, 5.5 g of anhydrouspotassium carbonate, and 40 mL of MIBK was added 2.49 g of3-chloromethyl-2,4-dimethyl-6-tert-butylphenol, 150 mg of sodium iodide,and 250 mg of Aliquat® 336. The reaction mixture was heated to refluxfor 8 hr. After 8 hr, TLC analysis showed almost no starting material.The reaction mixture was allowed to cool to room temperature, dilutedwith methylene chloride, and filtered through Celite® brand filteragent. The filtrate was concentrated under reduce pressure, to give amixture of Compounds W and X as determined by TLC.

Example 21 Preparation of2,4-bistetralin-6-(2,4-dihydroxy-3-diallylaminomethyl)-1,3,5-triazine(Compound Y)

To a stirring suspension of 2.2.5 g of Compound D in 50 mL of toluenewas added 3 mL of diallylamine and 5 mL of aqueous formaldehyde. Thereaction mixture was heated to reflux for 4 hr. After 4 hr, TLC analysisdetected almost no starting material and the formation of one majorproduct. The reaction mixture was allowed to cool to room temperatureand concentrated under reduced pressure. The residue was dissolved in100 mL of methylene chloride, washed with water, dried over anhydroussodium sulfate, and concentrated under reduce pressure to give CompoundX, which was analyzed by mass spectroscopy.

Example 22 Preparation of bis-tetralin-mono-resorcinol-1,3,5-triazinedimer (Compound Z)

To a mixture of 10 g of Compound D, 12.2 g of anhydrous potassiumcarbonate, 3.9 g of 1,5-diiodopentane, a catalytic amount of Aliquat®336, and 60 mL of dioxane was stirred at reflux for 24 hr. HPLC analysisindicated full conversion of compound D. After cooling, the mixture wasdiluted with 150 mL of methylene chloride and filtered through a bed ofdiatomaceous earth. The filtrate was concentrated under reduced pressureto give compound U.

Performance Testing Examples Example 23

3% Toluene solutions of the stabilizers were prepared. The colors ofthese solutions were measured in a 1-cm cell using a Byk-Gardner LiquidColor Spectrophotometer. As can be seen from Table I, tetralin triazineUV absorbers Compound E and Compound J have lower color than Tinuvin1577, a current art triazine UV absorber.

TABLE I Color Values Of 3% Toluene Solutions Of Stabilizers StabilizerAPHA Color Gardner Color CIE b value Tinuvin 1577 485 3 17.1 Compound E364 2 13.2 Compound O 218 1  7.9

Example 24

Thermogravimetric analysis was carried out. Duplicate specimens wereheated in a Perkin-Elmer 7 Series thermobalance from 30-500° C. at 10°C./ min in both air. The purge gas flow rate was ˜25 mL/min. Compound Ewas compared against the major current art stabilizers forpolycarbonate. As can be seen from Table II, Compound E is significantlyless volatile than Tinuvin 1577, a current art stabilizer. (T-10% andT-20% are the temperatures at which 10% and 20%, respectively, of weightloss occurs during the above heating protocol.)

TABLE II Thermogravimetric Data Stabilizer T-10% (° C.) T-20% (° C.)Tinuvin 1577 346 363 Tinuvin 234 310 331 Mixxim BB/100 359 382 CompoundE 419 440

Example 25

Polycarbonate plaques were prepared as follows. GE Lexan 105 barefootnatural flake polycarbonate resin (melt temperature 310-333° C.) was dryblended with 0.35% stabilizer plus 0.10 wt % Mark® 2112 phosphite. Theblended compositions were melt-mixed and extruded in a Haake torquerheometer equipped with a a 0.75-inch 25:1 single mixing screw extruder.The zone temperatures were 246, 265, 295, and 304° C. The extrudedpolycarbonate was pulled through a water bath, dried, pelletized, andredried at 120° C. for 4-48 hr in a forced air oven. The pellets wereinjection molded at 340° C. with a 40 second dwell time using an Arburg“Allrounder” hydraulic injection molder to form 2×2.5×0.100-inchplaques. The mold temperature was 100° C. The injection barreltemperature of 340° C. was selected to simulate extremely harshconditions. Yellow indices and delta E data were obtained using aMacbeth Color Eye Colorimeter with illuminate C, 2° observer, specularcomponent excluded, and UV component included. As can be seen from TableIII, Compound E is more resistant to thermal yellowing than Tinuvin1577, a current art triazine UV absorber.

TABLE III Color Of Stabilized Polycarbonate Plaques Injection Molded At340° C. Stabilizer Yellow Index Tinuvin 1577 14.5 Compound E 11.9

Example 26

Stabilized polycarbonate plaques were prepared as in Example 3 with theexception that the injection molding temperatures were lower. Thetemperatures were: nozzle—305° C.; nozzle side—310° C.; middle—300° C.;and feed—290° C. The plaques were subjected to 18 days of oven aging at100° C. As can be seen from Table IV, Compound E inhibits thermalyellowing of polycarbonate and has performance equal or better thancurrent art triazine UV absorbers Tinuvin 1577 and UV-1164.

TABLE IV Oven Aging of Stabilized Polycarbonate Compositions at 100° C.Delta E, Delta E, Stabilizer 7 days 18 days None 0.4 1.1 Compound E 0.50.4 Tinuvin 1577 0.5 0.5 UV-1164 0.4 0.6

Example 27

Stabilized polycarbonate plaques were prepared as in Example 4. Theywere exposed in a xenon-arc WeatherOmeter following ASTM G-26 using TestMethod B (Miami, Fla. conditions). The conditions were an irradiance of0.35 W/m² at 340 nm, alternating cycles of light and darkness,intermittent water spray, and a black panel temperature of 63±3° C.Delta E (total color change) was measured after 400 hr. of exposure. Theresults, summarized in Table V show that Compound E is more effective inreducing total color change than current art stabilizers Tinuvin 1577and Tinuvin 234.

TABLE V Accelerated Weathering of Stabilized Polycarbonate CompositionsStabilizer Delta E None 5.3 Compound E 0.6 Tinuvin 234 0.9 Tinuvin 15771.0

Example 28

Stabilized Coating Compositions

Stabilized clear acrylic melamine compositions were prepared and coatedonto steel panels for accelerated weathering testing as follows.Compound E (2% based on total resin solids) was pre-dissolved inxylenes, alone and in combination with Sanduvor® 3058 HALS (0.67% or1.0% based on total resin solids), and added to the clear acrylicmelamine formulation given in Table VI. Steel panels pre-coated withED5050A E-coat, 764204 primer, and 542DF716 white base-coat andmeasuring 4″×12″ were obtained from ACT Laboratories, Inc. (Hillsdale,Mich.). The panels were coated with the clear coat formulations usingthe draw-down technique (WC-52 Wire-Cators™ obtained from Leneta Colo.,Ho-Ho-Kus, N.J.). The clear coats were allowed to flash for 10 min. atambient temperature and cured for 30 min. at 135° C.

TABLE VI Acrylic Melamine Clear Coat Formulation Material AmountDoresco ® TA 39-14 acrylic resin 81.25 g Cymel ® 303 cross-linker 35.0 gCycat ® 4040 catalyst  1.0 g n-Butanol 20.0 g Xylene 16.0 g UV Absorber 0.364 g^(a) Sanduvor ® 3058^(b)  0.182 g^(b) ^(a)) Amount for 2% basedon total resin solids ^(b)) Amount for 1% based on total resin solids

Accelerated weathering is carried out with a QUV following ASTM G53 (GMcycle), which is weathering under alternate cycles of (i) UV light at 70C. for 8 hours and (ii) condensation with no UV light at 50 C. for 4 hr.Specular properties (gloss and distinctness of image, or DOI) aremeasured as a function of weathering time. Compositions containingeither Compound E or Compound J both have improved gloss and DOIretention relative to the unstabilized control. Compositions containingHALS S-3058 in addition to Compound E or Compound J also exhibitimproved gloss and DOI retention.

Although the present invention is described with reference to certainpreferred embodiments, it is apparent that modifications and variationsthereof may be made by those skilled in the art without departing fromthe scope and spirit of this invention as defined by the appendedclaims.

What is claimed is:
 1. A compound of formula (I)

wherein T is a direct bond, carbon, oxygen, nitrogen, sulfur, or afunctional group containing these elements; T′ is oxygen; X isindependently selected from hydrogen and a blocking group; each of R¹and R² is independently a hydrocarbyl group, a functional hydrocarbylgroup, hydroxy, —O(hydrocarbyl), hydrogen, halogen, cyano, or isocyanowherein the hydrocarbyl has 1 to 24 carbon atoms; each of Y, R³ and R⁴are independently a hydrogen, hydrocarbyl group, a functionalhydrocarbyl group, halogen, hydroxyl, cyano, —O(hydrocarbyl),—O(functional hydrocarbyl), —N(hydrocarbyl)₂, —N(functionalhydrocarbyl)₂, —N(hydrocarbyl)(functional hydrocarbyl), —S(hydrocarbyl),—S(functional hydrocarbyl), —SO₂(hydrocarbyl), —SO₂(functionalhydrocarbyl), —SO₃(hydrocarbyl), —SO₃(functional hydrocarbyl),—CO₂(hydrocarbyl), —CO₂(functional hydrocarbyl), —CO(hydrocarbyl),—CO(functional hydrocarbyl), —OCO(hydrocarbyl), —OCO(functionalhydrocarbyl), —CONH₂, —CONH(hydrocarbyl), —CONH(functional hydrocarbyl),—CON(hydrocarbyl)₂, —CON(hydrocarbyl)(functional hydrocarbyl), or—CON(functional hydrocarbyl)₂, wherein the hydrocarbyl or functionalhydrocarbyl may be the same or different and has 1 to 24 carbon atoms; Zis Y,

 wherein L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, ora functional hydrocarbyl group of 1 to 24 carbon atoms; X isindependently selected from hydrogen and a blocking group; and R³ and R⁴are independently hydrogen, hydrocarbyl, functional hydrocarbyl,halogen, hydroxyl, —O(hydrocarbyl), —O(functional hydrocarbyl),—S(hydrocarbyl), —SO₂(hydrocarbyl), —SO₃(hydrocarbyl),—CO₂(hydrocarbyl), —CO(hydrocarbyl), —OCO(hydrocarbyl),—N(hydrocarbyl)₂, —S(functional hydrocarbyl), —SO₂(functionalhydrocarbyl), —SO₃(functional hydrocarbyl), —CO₂(functionalhydrocarbyl), —CO(functional hydrocarbyl), —OCO(functional hydrocarbyl),—N(functional hydrocarbyl)₂ or cyano wherein the hydrocarbyl orfunctional hydrocarbyl may be the same or different and has 1 to 24carbon atoms; each G is independently a direct bond, nitrogen, sulfur,oxygen, or functional groups containing these elements; and each of m,n, and o is independently an integer between 0 and 4, provided that whenboth G are direct bonds, the sum of m, n and o is between 2 and 10, andthat when one G is a direct bond, the sum of m, n and o is between 1 and9, and when neither G is a direct bond, the sum of m, n and o is between0 and
 8. 2. A compound according to claim 1 wherein each G is a directbond; m is 4; n, o, p, and q are
 0. 3. A compound according to claim 1wherein T′ is an oxygen atom and Y is a group L, said compound havingformula (II):

wherein L is Y, L, T, X, Z, R¹, R², R³, R⁴, m, n, and o are as definedin claim
 1. 4. A compound according to claim 3 wherein L is selectedfrom the group consisting of hydrogen; an alkyl of 1 to 24 carbon atomsoptionally substituted by one or more hydroxy, alkoxy, carboxy,carboalkoxy, amino, amido, carbamato, or epoxy groups, and which maycontain one or more carbonyl groups, oxygen atoms or nitrogen atoms inthe chain; an alkenyl of 2 to 24 carbon atoms optionally substituted byone or more hydroxy, alkoxy, carboxy, carboalkoxy, amino, amido,carbamato, or epoxy groups, and which may contain one or more carbonylgroups, oxygen atoms or nitrogen atoms in the chain; an aralkyl of 7 to24 carbon atoms optionally substituted by one or more hydroxy, alkoxy,chloro, cyano, carboxy, carboalkoxy, amino, amido, carbamato, or epoxygroups, and which may contain one or more carbonyl groups, oxygen atomsor nitrogen atoms in the chain; a polyoxyalkylene radical of the formulaXII —CH₂—CH(OH)—CH₂—O—(CH₂—(CH₂)_(u)—O—)_(mm)—D₁  (XII) wherein D₁ ishydrogen, —CH₂—CH(OH)—CH₂—OH,

 or R²⁵; a polyoxyalkylene radical of the formula XIII—CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—D₂  (XIII) wherein D₂ is—(CH₂)_(u)—CO—R²² or R²⁵; a polyoxyalkylene radical of the formula VIII—YY—O—CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—D₃  (XIV) wherein D₃ is—(CH₂)_(u)—CO—R²² or R²⁵; a polyoxyalkylene radical of the formula XV—(CH₂)_(kk)—CH(R²¹)—CO—B₁—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—B₁—D₄  (XV)wherein D₄ is hydrogen of R²⁵; a polyoxyalkylene radical of the formulaXVI —CO—CH₂—CH₂—NH—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—D₅  (XVI)wherein D₅ is —NH₂, —NH—(CH₂)₂—COO—R²³ or —O—R²⁵; a polyoxyalkyleneradical of the formula XVII—YY—O—CO—CH₂—CH₂—NH—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—D₅  (XVII)wherein D₅ is as defined under formula (XVI); a polyoxyalkylene radicalof the formula XVIII —(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—D₆  (XVIII)wherein D₆ is —NH—CO—R²⁴, —OR²⁵, OH or H; a polyoxyalkylene radical ofthe formula XIX

 wherein D₇ is —OR²⁵, —NHCOR²⁴ or —OCH₂CH₂OR²⁵; R²¹ is hydrogen or C₁-C₆alkyl; R²² is halogen or —O—R²³; R²³ is hydrogen, C₁-C₆ alkyl, C₃-C₆alkenyl, aryl, or aryl-C₁-C₄-alkyl; R²⁴ is hydrogen, C₁-C₁₂ alkyl oraryl; R²⁵ is C₁-C₁₆ alkyl, C₅-C₁₂ cycloalkyl, C₃-C₆ alkenyl, C₁-C₁₂alkylaryl or aryl-C₁-C₄ alkyl; R²⁶ is hydrogen or C₁-C₄ alkyl; R²⁷ ishydrogen, C₁-C₁₈ alkyl, C₃-C₆ alkenyl, C₁-C₁₈ alkoxy, halogen oraryl-C₁-C₄-alkyl; R²⁸ and R²⁹ independently of one another are hydrogen,C₁-C₁₈ alkyl, C₃-C₆ alkenyl, C₁-C₁₈ alkoxy, or halogen; R³⁰ is hydrogen,C₁-C₄ alkyl or CN; YY is unsubstituted or substituted C₂-C₂₀ alkyl; kkis zero or an integer from 1-16; B₁ is O or NH; mm is an integer from 2to 60; nn is an integer from 2 to 6; and u is an integer from 1 to
 4. 5.A compound according to claim 3 wherein TZ is

wherein L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or afunctional hydrocarbyl group of 1 to 24 carbon atoms; X is independentlyselected from hydrogen and a blocking group; and R³ and R⁴ areindependently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen,hydroxyl, —O(hydrocarbyl), —O(functional hydrocarbyl), —S(hydrocarbyl),—SO₂(hydrocarbyl), —SO₃(hydrocarbyl), —CO₂(hydrocarbyl),—CO(hydrocarbyl), —OCO(hydrocarbyl), —N(hydrocarbyl)₂, —S(functionalhydrocarbyl), —SO₂(functional hydrocarbyl), —SO₃(functionalhydrocarbyl), —CO₂(functional hydrocarbyl), —CO(functional hydrocarbyl),—OCO(functional hydrocarbyl), —N(functional hydrocarbyl)₂ or cyanowherein the hydrocarbyl or functional hydrocarbyl may be the same ordifferent and has 1 to 24 carbon atoms.
 6. A compound according to claim5 wherein all G are direct bonds, m is 4, and n-o are 0, so that saidcompound has formula:

wherein L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or afunctional hydrocarbyl group of 1 to 24 carbon atoms; X is independentlyselected from hydrogen and a blocking group; and R³ and R⁴ areindependently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen,hydroxyl, —O(hydrocarbyl), —O(functional hydrocarbyl), —S(hydrocarbyl),—SO₂(hydrocarbyl), —SO₃(hydrocarbyl), —CO₂(hydrocarbyl),—CO(hydrocarbyl), —OCO(hydrocarbyl), —N(hydrocarbyl)₂, —S(functionalhydrocarbyl), —SO₂(functional hydrocarbyl), —SO₃(functionalhydrocarbyl), —CO₂(functional hydrocarbyl), —CO(functional hydrocarbyl),—OCO(functional hydrocarbyl), —N(functional hydrocarbyl)₂ or cyanowherein the hydrocarbyl or functional hydrocarbyl may be the same ordifferent and has 1 to 24 carbon atoms.
 7. A compound according to claim1 wherein T is a direct bond and Z is:

so that said compound has formula:

wherein G, L, T′, X, Y, R¹ to R⁴, and subscripts m, n, o, p, and q, aredefined as in claim
 1. 8. A compound according to claim 7 wherein all Gare direct bonds; m=4; and n, o, are 0; said compound having formula:

wherein L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or afunctional hydrocarbyl group of 1 to 24 carbon atoms; X is independentlyselected from hydrogen and a blocking group; and R³ and R⁴ areindependently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen,hydroxyl, —O(hydrocarbyl), —O(functional hydrocarbyl), —S(hydrocarbyl),—SO₂(hydrocarbyl), —SO₃(hydrocarbyl), —CO₂(hydrocarbyl),—CO(hydrocarbyl), —OCO(hydrocarbyl), —N(hydrocarbyl)₂, —S(functionalhydrocarbyl), —SO₂(functional hydrocarbyl), —SO₃(functionalhydrocarbyl), —CO₂(functional hydrocarbyl), —CO(functional hydrocarbyl),—OCO(functional hydrocarbyl), —N(functional hydrocarbyl)₂ or cyanowherein the hydrocarbyl or functional hydrocarbyl may be the same ordifferent and has 1 to 24 carbon atoms.
 9. A compound of formula (VII):

wherein T, T′, R¹, R², Y, Z, R³, R⁴, G, m, n, o, are defined as in claim1; r is 2 or 3; when r is 2, X′ is —CO—R¹⁶—CO—, —CO₂—R¹⁶—CO₂—,—SO₂—R¹⁶—SO₂—, —CO—NH—R¹⁷—NH—CO—, a polyoxyalkylene bridge member offormula —CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—(CH₂)_(u)—CO—, or

when r=3, X′ is: —(—CO₂—R¹⁶)R¹⁹, —(—CONH—R¹⁶)R¹⁹, —(—SO₂—R¹⁶)R¹⁹; R¹⁶ isC₂-C₁₀ alkylene, C₂-C₁₀ oxaalkylene or C₂-C₁₀ dithiaalkylene, phenylene,naphthylene, diphenylene or C₂-C₆ alkenylene; R¹⁷ is C₂-C₁₀ alkylene,phenylene, naphthylene, methylenediphenylene or C₇-C₁₅ alkylphenylene;and R¹⁸ is C₂-C₁₀ alkylene or C₄-C₂₀ alkylene which is interrupted byone or more oxygen atoms; R¹⁹ is C₃-C₁₀alkanetriyl; and R²⁰ isC₄-C₁₀alkanetetryl.
 10. A compound of formula (VI):

wherein T, X, Z, R¹, R², R³, R⁴, G, m, n, o, are defined as in claim 1;r is an integer between 2 and 4; when r is 2, D is selected from thegroup consisting of C₂-C₁₆ alkyl, C₄-C₁₂ alkenyl, xylylene, C₃-C₂₀ alkylwhich is interrupted by one or more oxygen atoms, hydroxy-substitutedC₃-C₂₀ alkyl which is interrupted by one or more oxygen atoms,—CH₂CH(OH)CH₂O—R¹⁵—OCH₂CH(OH)CH₂, —CO—R¹⁶—CO—, —CO—NH—R¹⁷—NH—CO—,—(CH₂)_(s)—COO—R¹⁸—OCO—(CH₂)_(s)— a polyoxyalkylene bridge member of theformula XX—CH₂—CH(OH)—CH₂—O—(CH₂—(CH₂)_(u)—O—)_(mm)—CH₂—CH(OH)—CH₂—  (XX),  apolyoxyalkylene bridge member of the formula XX—CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—(CH₂)_(u)—CO—  (XXI),  apolyoxyalkylene bridge member of the formula XXII—YY—O—CO(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—(CH₂)_(u)—COO—YY—  (XXII), a polyoxyalkylene bridge member of the formula XXIII—(CH₂)_(kk)—CH(R²¹)—CO—B_(1\)—(C_(nn)H_(2nn)—O—)_(mm)C_(nn)H_(2nn)—B₁—CO—CH(R²¹)—(CH₂)_(kk)—  (XXIII), a polyoxyalkylene bridge member of the formula XXIV

 a polyoxyalkylene bridge member of the formula XXV—YY—O—CO—(CH₂)₂—NH—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—NH—(CH₂)₂COO—YY—  (XXV), a polyoxyalkylene bridge member of the formula XXVI—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—  (XXVI),  and a polyoxyalkylenebridge member of the formula XXVII—CH(CH₃)—CH₂—(O—CH(CH₃)—CH₂)_(a)—(O—CH₂—CH₂)_(b)—(O—CH₂—CH(CH₃)_(c)—  (XXVI), wherein a+c=2.5 and b=8.5 to 40.5 or a+c=2 to 33 and b=0, R²¹ ishydrogen or C₁-C₁₆ alkyl, R²² is halogen or —O—R²³, R²³ is hydrogen,C₁-C₆ alkyl, C₃-C₆ alkenyl, aryl, or aryl-C₁-C₄-alkyl, R²⁴ is hydrogen,C₁-C₁₂ alkyl or aryl, R²⁵ is C₁-C₁₆ alkyl, C₅-C₁₂ cycloalkyl, C₃-C₆alkenyl, C₁-C₁₂ alkylaryl or aryl-C₁-C₄ alkyl, R²⁶ is hydrogen or C₁-C₄alkyl, R²⁷ is hydrogen, C₁-C₁₈ alkyl, C₃-C₆ alkenyl, C₁-C₁₈ alkoxy,halogen or aryl-C₁-C₄ alkyl, R²⁸ and R²⁹ independently of one anotherare hydrogen, C₁C₁₈ alkyl, C₃-C₆ alkenyl, or C₁-C₁₈ alkoxy, or halogen;R³⁰ is hydrogen, C₁-C₄ alkyl or CN, YY is unsubstituted or substitutedC₂-C₂₀ alkyl, kk is zero or an integer from 1-16, B₁ is O or NH, mm isan integer from 2 to 60, nn is an integer from 2 to 6, u is an integerfrom 1 to 4; when r is 3, D is

and when r is 4, D is

 wherein R¹⁹ is C₃-C₁₀ alkanetriyl and R²⁰ is C₄-C₁₀ alkanetetryl; and sis 1-6; R¹⁵ is C₂-C₁₀ alkyl, C₂-C₁₀ oxaalkyl or C₂-C₁₀ dithiaalkyl,phenyl, naphthyl, diphenyl, or C₂-C₆ alkenyl, or phenylene-XX-phenylenewherein XX is —O—, —S—, —SO₂—, —CH₂—, or —C(CH₃)₂—; R¹⁶ is C₂-C₁₀ alkyl,C₂-C₁₀ oxaalkyl or C₂-C₁₀ dithiaalkyl, phenyl, naphthyl, diphenyl, orC₂-C₆ alkenyl provided that when r is 3 the alkenyl has at least 3carbons; R¹⁷ is C₂-C₁₀ alkyl, phenyl, naphthyl, diphenyl, or C₂-C₆alkenyl, methylenediphenylene, or C₄-C₁₅ alkylphenyl; and R¹⁸ is C₂-C₁₀alkyl, or C₄-C₂₀ alkyl interrupted by one or more oxygen atoms.
 11. Acompound of formula (IX):

wherein T, T′, X, Y, R¹, R², R³, R⁴, G, m, n, o, are defined as in claim1; r is an integer between 2 and 4; when r is 2, D is selected from thegroup consisting of C₂-C₁₆ alkylene, C₄-C₁₂ alkenylene, xylylene, C₃-C₂₀alkylene which is interrupted by one or more oxygen atoms,hydroxy-substituted C₃-C₂₀ alkylene which is interrupted by one or moreoxygen atoms, —OOCR¹⁴COO—, —CH₂CH(OH)CH₂O—R¹⁵—OCH₂CH(OH)CH₂,—CO—R¹⁶—CO—, —CO—NH—R¹⁷—NH—CO—, and —(CH₂)_(s)—COO—R¹⁸—OCO—(CH₂)_(s)—;and when r is 3, D is

and when r is 4, D is

wherein R¹⁹ is C₃-C₁₀ alkanetriyl and R²⁰ is C₄-C₁₀ alkanetetryl; s is1-6; r is an integer between 2 and 4; when r is 2, D is selected fromthe group consisting of C₂-C₁₆ alkylene, C₄-C₁₂ alkenylene, xylylene,C₃-C₂₀ alkylene which is interrupted by one or more oxygen atoms,hydroxy-substituted C₃-C₂₀ alkylene which is interrupted by one or moreoxygen atoms, —CH₂CH(OH)CH₂O—R¹⁵—OCH₂CH(OH)CH₂, —CO—R¹⁶—CO—,—CO—NH—R¹⁷—NH—CO—, and —(CH₂)_(s)—COO—R¹⁸—OCO—(CH₂)_(s)—; and when r is3, D is

and when r is 4, D is

 wherein R¹⁹ is C₃-C₁₀ alkanetriyl and R²⁰ is C₄-C₁₀ alkanetetryl; s is1-6; R⁸ is C₁-C₁₈ alkyl, C₃-C₁₈ alkenyl, C₃-C₂₀ alkyl, which isinterrupted by O, N, or S, and/or substituted by OH, C₁-C₄ alkyl whichis substituted by —P(O)(OR¹⁴)₂, —N(R⁹) (R¹⁰), or —OCOR¹¹, and/or OH, oris glycidyl, cyclohexyl or C₇-C₁₁ phenylalkyl; R⁹ and R¹⁰ are eachindependently of the other, C₁-C₁₂ alkyl, C₃-C₁₂ alkoxyalkyl, C₄-C₁₆dialkylaminoalkyl or C₅-C₁₂ cycloalkyl, or R⁹ and R¹⁰, when takentogether, are C₃-C₉ alkylene or C₃-C₉ oxaalkylene of C₃-C₉ azaalkylene;R¹¹ is C₁-C₁₈ alkyl, C₂-C₁₈ alkenyl or phenyl; R¹² is C₁-C₁₈ alkyl,C₂-C₁₈ alkenyl, phenyl, C₁-C₁₂ alkoxy, phenoxy, C₁-C₁₂ alkylamino;phenylamino, tolylamino or naphthylamino; R¹³ is C₁-C₁₂ alkyl, phenyl,naphthyl or C₇-C₁₄ alkylphenyl; R¹⁴ is C₁-C₁₂ alkyl or phenyl; R¹⁵ isC₂-C₁₀ alkylene phenylene or a phenylene-x-phenylene-group, wherein X is—O—, —S—, —SO₂—, —CH₂—, or —C(CH₃)₂—; R¹⁶ is C₂-C₁₀ alkylene, C₂-C₁₀oxaalkylene or C₂-C₁₀ dithiaalkylene, phenylene, naphthylene,diphenylene or C₂-C₆ alkenylene; R¹⁷ is C₂-C₁₀ alkylene, phenylene,naphthylene, methylenediphenylene or C₇-C₁₅ alkylphenylene, and R¹⁸ isC₂-C₁₀ alkylene or C₄-C₂₀ alkylene which is interrupted by one or moreoxygen atoms.
 12. A compound according to claim 9 wherein T is a directbond and Z is a substituent of general formula III:

wherein L is hydrogen, a hydrocarbyl group of 1 to 24 carbon atoms, or afunctional hydrocarbyl group of 1 to 24 carbon atoms; X is independentlyselected from hydrogen and a blocking group; and R³ and R⁴ areindependently hydrogen, hydrocarbyl, functional hydrocarbyl, halogen,hydroxyl, —O(hydrocarbyl), —O(functional hydrocarbyl), —S(hydrocarbyl),—SO₂(hydrocarbyl), —SO₃(hydrocarbyl), —CO₂(hydrocarbyl),—CO(hydrocarbyl), —OCO(hydrocarbyl), —N(hydrocarbyl)₂, —S(functionalhydrocarbyl), —SO₂(functional hydrocarbyl), —SO₃(functionalhydrocarbyl), —CO₂(functional hydrocarbyl), —CO(functional hydrocarbyl),—OCO(functional hydrocarbyl), —N(functional hydrocarbyl)₂ or cyanowherein the hydrocarbyl or functional hydrocarbyl may be the same ordifferent and has 1 to 24 carbon atoms.
 13. A compound according toclaim 10 wherein T is a direct bond and Z is a substituent of generalformula III:

wherein R¹, R², G, m, n, o, are defined as in claim 10; L is hydrogen, ahydrocarbyl group of 1 to 24 carbon atoms, or a functional hydrocarbylgroup of 1 to 24 carbon atoms; X is independently selected from hydrogenand a blocking group; and R³ and R⁴ are independently hydrogen,hydrocarbyl, functional hydrocarbyl, halogen, hydroxyl, —O(hydrocarbyl),—O(functional hydrocarbyl), —S(hydrocarbyl), —SO₂(hydrocarbyl),—SO₃(hydrocarbyl), —CO₂(hydrocarbyl), —CO(hydrocarbyl),—OCO(hydrocarbyl), —N(hydrocarbyl)₂, —S(functional hydrocarbyl),—SO₂(functional hydrocarbyl), —SO₃(functional hydrocarbyl),—CO₂(functional hydrocarbyl), —CO(functional hydrocarbyl),—OCO(functional hydrocarbyl), —N(functional hydrocarbyl)₂ or cyanowherein the hydrocarbyl or functional hydrocarbyl may be the same ordifferent and has 1 to 24 carbon atoms.
 14. A compound according toclaim 12 wherein L is selected from the group consisting of hydrogen; analkyl of 1 to 24 carbon atoms optionally substituted by one or morehydroxyl, carboxyl, carboalkoxy, amide, epoxy or amino groups andoptionally containing one or more carbonyl groups, oxygen atoms ornitrogen atoms in the chain; an alkenyl of 2 to 24 carbon atomsoptionally substituted by hydroxyl, carboxyl, epoxy or amino group(s)and optionally containing one or more carbonyl groups, oxygen ornitrogen atoms in the chain; a cycloalkyl of 5 to 24 carbon atomsoptionally substituted by hydroxyl, carboxyl, or amino group(s), andoptionally containing carbonyl, oxygen, or nitrogen in the ring; and anaralkyl of 7 to 24 carbon atoms optionally substituted by hydroxyl,carboxyl or amino group(s) and may contain carbonyl, oxygen and/ornitrogen in the ring; a polyoxyalkylene radical of the formula XII—CH₂—CH(OH)—CH₂—O—(CH₂—(CH₂)_(u)—O—)_(mm)—D₁ wherein D₁ is hydrogen,—CH₂—CH(OH)—CH₂—OH,

 or R²⁵; a polyoxyalkylene radical of the formula XIII—CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—D₂ wherein D₂ is—(CH₂)_(u)—CO—R²² or R²⁵; a polyoxyalkylene radical of the formula VIII—YY—O—CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—D₃ wherein D₃ is—(CH₂)_(u)—CO—R²² or R²⁵; a polyoxyalkylene radical of the formula XV—(CH₂)_(kk)—CH(R²¹)—CO—B₁—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—B₁—D₄wherein D₄ is hydrogen of R²⁵; a polyoxyalkylene radical of the formulaXVI —CO—CH₂—CH₂—NH—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—D₅ wherein D₅is —NH₂, —NH—(CH₂)₂—COO—R²³ or —O—R²⁵; a polyoxyalkylene radical of theformula XVII—YY—O—CO—CH₂—CH₂—NH—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—D₅ wherein D₅is as defined under formula XVI; a polyoxyalkylene radical of theformula XVIII —(C_(nn)H_(2nn)—O—)_(mm)C_(nn)H_(2nn)—D₆ wherein D₆ is—NH—CO—R²⁴, —OR²⁵, OH or H; a polyoxyalkylene radical of the formula XIX

 wherein D₇ is —OR²⁵, —NHCOR²⁴ or —OCH₂CH₂OR²⁵; a polyoxyalkylene bridgemember of the formula XX—CH₂—CH(OH)—CH₂—O—(CH₂—(CH₂)_(u)—O—)_(mm)—CH₂—CH(OH)—CH₂—; apolyoxyalkylene bridge member of the formula XXI—CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—(CH₂)_(u)—CO—; a polyoxyalkylenebridge member of the formula XXII—YY—O—CO(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—(CH₂)_(u)—COO—YY—; apolyoxyalkylene bridge member of the formula XXIII—(CH₂)_(kk)—CH(R²¹)—CO—B₁—(C_(nn)H_(2nn)—O—)_(mm)C_(nn)H_(2nn)—B₁—CO—CH(R²¹)—(CH₂)_(kk)—;a polyoxyalkylene bridge member of the formula XXIV

a polyoxyalkylene bridge member of the formula XXV—YY—O—CO—(CH₂)₂—NH—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—NH—(CH₂)₂COO—YY—;a polyoxyalkylene bridge member of the formula XXVI—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—; a polyoxyalkylene bridge memberof the formula XXVII—CH(CH₃)—CH₂—(O—CH(CH₃)—CH₂)_(a)—(O—CH₂—CH₂)_(b)—(O—CH₂—CH(CH₃)_(c)— wherein a+c=2.5 and b=8.5 to 40.5, or a+c=2 to 33 and b=0; R²¹ ishydrogen or C₁-C₁₆ alkyl; R²² is halogen or —O—R²³; R²³ is hydrogen,C₁-C₆alkyl, C₃-C₆ alkenyl, aryl, or aryl-C₁-C₄-alkyl; R²⁴ is hydrogen,C₁-C₁₂ alkyl or aryl; R²⁵ is C₁-C₁₆ alkyl, C₅-C₁₂ cycloalkyl, C₃-C₆alkenyl, C₁-C₁₂ alkylaryl or aryl-C₁-C₄ alkyl; R²⁶ is hydrogen or C₁-C₄alkyl; R²⁷ is hydrogen, C₁-C₁₈ alkyl, C₃-C₆ alkenyl, C₁-C₁₈ alkoxy,halogen or aryl-C₁-C₄ alkyl; R²⁸ and R²⁹ independently of one anotherare hydrogen, C₁-C₁₈ alkyl, C₃-C₆ alkenyl, C₁-C₁₈ alkoxy or halogen; R³⁰is hydrogen, C₁-C₄ alkyl

 or CN; YY is unsubstituted or substituted C₂-C₂₀ alkylene; kk is zeroor an integer from 1-16; mm is an integer from 2 to 60; nn is an integerfrom 2 to 6; and u is an integer from 1 to
 4. 15. A compound accordingto claim 13 wherein L is selected from the group consisting of hydrogen;an alkyl of 1 to 24 carbon atoms optionally substituted by one or morehydroxyl, carboxyl, carboalkoxy, amide, epoxy or amino groups andoptionally containing one or more carbonyl groups, oxygen atoms ornitrogen atoms in the chain; an alkenyl of 2 to 24 carbon atomsoptionally substituted by hydroxyl, carboxyl, epoxy or amino group(s)and optionally containing one or more carbonyl groups, oxygen ornitrogen atoms in the chain; a cycloalkyl of 5 to 24 carbon atomsoptionally substituted by hydroxyl, carboxyl, or amino group(s), andoptionally containing carbonyl, oxygen, or nitrogen in the ring; and anaralkyl of 7 to 24 carbon atoms optionally substituted by hydroxyl,carboxyl or amino group(s) and may contain carbonyl, oxygen and/ornitrogen in the ring; a polyoxyalkylene radical of the formula XII—CH₂—CH(OH)—CH₂—O—(CH₂—(CH₂)_(u)—O—)_(mm)—D₁ wherein D₁ is hydrogen,—CH₂—CH(OH)—CH₂—OH,

 or R²⁵; a polyoxyalkylene radical of the formula XIII—CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—D₂ wherein D₂ is—(CH₂)_(u)—CO—R²² or R²⁵; a polyoxyalkylene radical of the formula VIII—YY—O—CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—D₃ wherein D₃ is—(CH₂)_(u)—CO—R²² or R²⁵; a polyoxyalkylene radical of the formula XV—(CH₂)_(kk)—CH(R²¹)—CO—B₁—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—B₁—D₄wherein D₄ is hydrogen of R²⁵; a polyoxyalkylene radical of the formulaXVI —CO—CH₂—CH₂—NH—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—D₅ wherein D₅is —NH₂, —NH—(CH₂)₂—COO—R²³ or —O—R²⁵; a polyoxyalkylene radical of theformula XVII—YY—O—CO—CH₂—CH₂—NH—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—D₅ wherein D₅is as defined under formula XVI; a polyoxyalkylene radical of theformula XVIII —(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—D₆ wherein D₆ is—NH—CO—R²⁴, —OR²⁵, OH or H; a polyoxyalkylene radical of the formula XIX

 wherein D₇ is —OR²⁵, —NHCOR²⁴ or —OCH₂CH₂OR²⁵; a polyoxyalkylene bridgemember of the formula XX—CH₂—CH(OH)—CH₂—O—(CH₂—(CH₂)_(u)—O—)_(mm)—CH₂—CH(OH)—CH₂—; apolyoxyalkylene bridge member of the formula XXI—CO—(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—(CH₂)_(u)—CO—; a polyoxyalkylenebridge member of the formula XXII—YY—O—CO(CH₂)_(u)—O—(CH₂—(CH₂)_(u)—O—)_(mm)—(CH₂)_(u)—COO—YY—; apolyoxyalkylene bridge member of the formula XXIII—(CH₂)_(kk)—CH(R²¹)—CO—B₁—(C_(nn)H_(2nn)—O—)_(mm)C_(nn)H_(2nn)—B₁—CO—CH(R²¹)—(CH₂)_(kk)—;a polyoxyalkylene bridge member of the formula XXIV

a polyoxyalkylene bridge member of the formula XXV —YY—O—CO—(CH₂)₂—NH—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—NH—(CH₂)₂COO—YY—;a polyoxyalkylene bridge member of the formula XXVI—(C_(nn)H_(2nn)—O—)_(mm)—C_(nn)H_(2nn)—; a polyoxyalkylene bridge memberof the formula XXVII—CH(CH₃)—CH₂—(O—CH(CH₃)—CH₂)_(a)—(O—CH₂—CH₂)_(b)—(O—CH₂—CH(CH₃)_(c)— wherein a+c=2.5 and b=8.5 to 40.5, or a+c=2 to 33 and b=0; R²¹ ishydrogen or C₁-C₁₆ alkyl; R²² is halogen or —O—R²³; R²³ is hydrogen,C₁-C₆ alkyl, C₃-C₆ alkenyl, aryl, or aryl-C₁-C₄-alkyl; R²⁴ is hydrogen,C₁-C₁₂ alkyl or aryl; R²⁵ is C₁-C₁₆ alkyl, C₅-C₁₂ cycloalkyl, C₃-C₆alkenyl, C₁-C₁₂ alkylaryl or aryl-C₁-C₄alkyl; R²⁶ is hydrogen or C₁-C₄alkyl; R²⁷ is hydrogen, C₁-C₁₈ alkyl, C₃-C₆ alkenyl, C₁-C₁₈ alkoxy,halogen or aryl-C₁-C₄ alkyl; R²⁸ and R²⁹ independently of one anotherare hydrogen, C₁-C₁₈ alkyl, C₃-C₆ alkenyl, C₁-C₁₈ alkoxy or halogen; R³⁰is hydrogen, C₁-C₄ alkyl or CN; YY is unsubstituted or substitutedC₂-C₂₀ alkylene; kk is zero or an integer from 1-16; mm is an integerfrom 2 to 60; nn is an integer from 2 to 6; and u is an integer from 1to
 4. 16. A compound of formula (VIII):

wherein T, T′, X, Y, Z, R¹, R², R³, G, m, n, and o are as defined inclaim 1; R⁴ is selected from the group consisting of straight chainalkylene of 1 to 12 carbon atoms, branched chain alkylene of 1 to 12carbon atoms, cycloalkylene of 5 to 12 carbon atoms, alkylenesubstituted by cyclohexyl, alkylene interrupted by cyclohexyl, alkylenesubstituted by phenylene, alkylene interrupted by phenylene,benzylidene, —S—, —S—S—, —S—E—S—, —SO—, —SO₂—, —SO—E—SO—, —SO₂—E—SO₂—,—CH₂—NH—E—NH—CH₂—, and

 wherein E is selected from the group consisting of alkylene of 2 to 12carbon atoms, cycloalkylene of 5 to 12 carbon atoms, alkyleneinterrupted by cyclohexylene of 8 to 12 carbon atoms, alkyleneterminated by cyclohexylene of 8 to 12 carbon atoms; and r is an integerbetween 2 and
 4. 17. A compound of the formula:

wherein X is independently selected from hydrogen and a blocking group;and L, R³ and R⁴ are independently hydrogen, hydrocarbyl, functionalhydrocarbyl, halogen, hydroxyl, —O(hydrocarbyl), —O(functionalhydrocarbyl), —S(hydrocarbyl), —SO₂(hydrocarbyl), —SO₃(hydrocarbyl),—COO(hydrocarbyl), —CO(hydrocarbyl), —OCO(hydrocarbyl),—N(hydrocarbyl)(hydrocarbyl), —S(functional hydrocarbyl),—SO₂(functional hydrocarbyl), —SO₃(functional hydrocarbyl),—COO(functional hydrocarbyl), —CO(functional hydrocarbyl),—OCO(functional hydrocarbyl), —N(functional hydrocarbyl)(functionalhydrocarbyl) or cyano wherein the hydrocarbyl or functional hydrocarbylmay be the same or different and has 1 to 24 carbon atoms.
 18. Acompound of formula (XXXVII)

wherein each of T is independently a direct bond, carbon, oxygen,nitrogen, sulfur, or functional groups containing these elements; eachof Z are independently a hydrogen, hydrocarbyl group, a functionalhydrocarbyl group, halogen, hydroxyl, cyano, —O(hydrocarbyl),—O(functional hydrocarbyl), —N(hydrocarbyl)₂, —N(functionalhydrocarbyl)₂, —N(hydrocarbyl)(functional hydrocarbyl), —S(hydrocarbyl),—S(functional hydrocarbyl), —SO₂(hydrocarbyl), —SO₂(functionalhydrocarbyl), —SO₃(hydrocarbyl), —SO₃(functional hydrocarbyl),—CO₂(hydrocarbyl), —CO₂(functional hydrocarbyl), —CO(hydrocarbyl),—CO(functional hydrocarbyl), —OCO(hydrocarbyl), —OCO(functionalhydrocarbyl), —CONH₂, —CONH(hydrocarbyl), —CONH(functional hydrocarbyl),—CON(hydrocarbyl)₂, —CON(hydrocarbyl)(functional hydrocarbyl), or—CON(functional hydrocarbyl)₂, wherein the hydrocarbyl or functionalhydrocarbyl may be the same or different and has 1 to 24 carbon atoms.19. A compound of formula (XXXVIII)

wherein T is a direct bond, carbon, oxygen, nitrogen, sulfur, or afunctional group containing these elements; Z is a hydrogen, hydrocarbylgroup, a functional hydrocarbyl group, halogen, hydroxyl, cyano,—O(hydrocarbyl), —O(functional hydrocarbyl), —N(hydrocarbyl)₂,—N(functional hydrocarbyl)₂, —N(hydrocarbyl)(functional hydrocarbyl),—S(hydrocarbyl), —S(functional hydrocarbyl), —SO₂(hydrocarbyl),—SO₂(functional hydrocarbyl), —SO₃(hydrocarbyl), —SO₃(functionalhydrocarbyl), —CO₂(hydrocarbyl), —CO₂(functional hydrocarbyl),—CO(hydrocarbyl), —CO(functional hydrocarbyl), —OCO(hydrocarbyl),—OCO(functional hydrocarbyl), —CONH₂, —CONH(hydrocarbyl),—CONH(functional hydrocarbyl), —CON(hydrocarbyl)₂,—CON(hydrocarbyl)(functional hydrocarbyl), or —CON(functionalhydrocarbyl)₂, wherein the hydrocarbyl or functional hydrocarbyl may bethe same or different and has 1 to 24 carbon atoms.
 20. A compound ofthe formula S:


21. A compound of the formula T: